Silicone structure-bearing polymer, negative resist composition, photo-curable dry film, patterning process, and electric/electronic part-protecting film

Patent metadata

Field	Value
Publication number	US-9377689-B2
Application number	US-201514807072-A
Country	US
Kind code	B2
Filing date	Jul 23, 2015
Priority date	Jul 29, 2014
Publication date	Jun 28, 2016
Grant date	Jun 28, 2016

Abstract

A silicone structure-bearing polymer comprising recurring units derived from a bis(4-hydroxy-3-allylphenyl) derivative and having a Mw of 3,000-500,000 is provided. A chemically amplified negative resist composition comprising 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 silicone structure-bearing polymer comprising recurring units of the general formula (1) and having a weight average molecular weight of 3,000 to 500,000,

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, and a+b+c+d+e+f=1,
X is an organic group having the general formula (2):

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

the broken line segment denotes a valence bond, 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 or 2,
Y is an organic group having the general formula (3):

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

the broken line segment denotes a valence bond, 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 an organic group having the general formula (4):

wherein the broken line segment denotes a valence bond, R is hydrogen or a straight or branched C 1 -C 6 alkyl group, and T is a straight, branched or cyclic C 1 -C 12 alkylene group.

2. The polymer of claim 1 wherein W is an organic group having the general formula (5):

3. The polymer of claim 1 wherein in formula (1), 0.1≦a≦0.8, 0.1≦b≦0.8, 0≦c, 0≦d, 0<e≦0.8, and 0<f≦0.8.

4. A chemically amplified negative resist composition comprising
(A) the silicone structure-bearing polymer having a weight average molecular weight of 3,000 to 500,000, of claim 1 ,
(B) a photoacid generator which is decomposed to generate an acid upon exposure to radiation of wavelength 190 to 500 nm,
(C) 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, a polyhydric phenol compound in which at least one hydrogen atom of hydroxyl group is substituted by a glycidyl group, a polyhydric phenol compound in which at least one hydrogen atom of hydroxyl group is substituted by a group of the formula (C-1), and a compound containing at least two structures each having nitrogen bonded to a glycidyl group, the structure having the formula (C-2) or (C-3),

wherein the broken line segment denotes a valence bond, Rc is a straight, branched or cyclic C 1 -C 6 alkyl group, and s is 1 or 2, and
(D) a solvent.

5. A pattern forming process comprising the steps of:
(1) coating the chemically amplified negative resist composition of claim 4 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.

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

7. An electric/electronic part protective film comprising the post-cured patterned resist film obtained by the process of claim 6 .

8. 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 the chemically amplified negative resist composition of claim 4 .

9. A method for preparing a photo-curable dry film, comprising the steps of:
(i) continuously coating the chemically amplified negative resist composition of claim 4 onto a support film,
(ii) continuously drying the composition to form a photo-curable resin layer on the support film, and
(iii) applying a protective film onto the photo-curable resin layer.

10. A pattern forming process comprising the steps of:
(i) stripping the protective film from the photo-curable dry film of claim 8 and placing the bare photo-curable resin layer in close contact with a substrate,
(ii) exposing the photo-curable resin layer to high-energy radiation of wavelength 190 to 500 nm or EB 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.

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

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

13. 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 μm, and
a layer lying on the substrate, the layer being a photo-curable resin layer formed of the chemically amplified negative resist composition of claim 10 .

14. A bis(4-hydroxy-3-allylphenyl) derivative having an alcoholic hydroxyl group, represented by the general formula (6):

wherein R is hydrogen or a straight or branched C 1 -C 6 alkyl group and T is a straight, branched or cyclic C 1 -C 12 alkylene group.

15. 4,4-bis(4-hydroxy-3-allylphenyl)pentanol represented by the formula (7):

Assignees

• Shinetsu Chemical Co

Inventors

• Takemura Katsuya
• Urano Hiroyuki
• Iio Masashi
• Fujiwara Takayuki
• Hasegawa Koji

Classifications

• H10P95/00

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

• C08L83/14

  in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C08L83/10 takes precedence) · CPC title

• G03F7/0382

  the macromolecular compound being present in a chemically amplified negative photoresist composition · 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

• G03F7/0757 Primary

  Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence) · CPC title