Silicone skeleton-containing polymer compound and method for producing same, chemically amplified negative resist composition, photo-curable dry film and method for producing same, patterning process, layered product, and substrate

Patent metadata

Field	Value
Publication number	US-10114287-B2
Application number	US-201514855163-A
Country	US
Kind code	B2
Filing date	Sep 15, 2015
Priority date	Oct 2, 2014
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

The present invention provides a silicone skeleton-containing polymer compound containing a repeating unit shown by the general formula (1) and having a weight average molecular weight of 3,000 to 500,000. There can be provided a silicone skeleton-containing polymer compound suitable used as a base resin of a chemically amplified negative resist composition that can remedy the problem of delamination generated on a metal wiring such as Cu and Al, an electrode, and a substrate, especially on a substrate such as SiN, and can form a fine pattern without generating a scum and a footing profile in the pattern bottom and on the substrate when the widely used 2.38% TMAH aqueous solution is used as a developer.

First claim

What is claimed is:

1. A silicone skeleton-containing polymer compound comprising a repeating unit shown by the general formula (1) and having a weight average molecular weight of 3,000 to 500,000,

wherein R 1 to R 4 may be the same or different and represent a monovalent hydrocarbon group having 1 to 8 carbon atoms; “m” is an integer of 1 to 100; “a”, “b”, “c”, “d”, “e”, and “f” are each 0 or a positive number, and “g” and “h” are each a positive number, provided that a+b+c+d+e+f+g+h=1; X is a divalent organic group shown by the general formula (2); Y is a divalent organic group shown by the general formula (3); W is a divalent organic group shown by the general formula (4); and U is a divalent organic group shown by the general formula (5),

wherein Z represents a divalent organic group selected from any of

the dotted line represents a bond; “n” is 0 or 1; R 5 and R 6 each represent an alkyl group or alkoxy group having 1 to 4 carbon atoms and may be the same or different; and “x” is 0, 1, or 2;

wherein V represents a divalent organic group selected from any of

the dotted line represents a bond; “p” is 0 or 1; R 7 and R 8 each represent an alkyl group or alkoxy group having 1 to 4 carbon atoms and may be the same or different; and “y” is 0, 1, or 2;

wherein the dotted line represents a bond; T represents an alkylene group having 1 to 10 carbon atoms or a divalent aromatic group; and R 9 represents a hydrogen atom or a methyl group;

wherein the dotted line represents a bond; T and R 9 have the same meanings as defined above; and R 10 represents a monovalent carboxyl-containing organic group.

2. The silicone skeleton-containing polymer compound according to claim 1 , wherein R 10 in the general formula (5) is a monovalent carboxyl-containing organic group shown by the general formula (6),

wherein the dotted line represents a bond; R 11 to R 14 may be the same or different and represent a hydrogen atom, a halogen atom, a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, or an aromatic group; R 11 and R 13 may be bonded respectively to R 12 and R 14 to form a substituted or unsubstituted ring structure having 1 to 12 carbon atoms; and “j” is any of 1 to 7.

3. The silicone skeleton-containing polymer compound according to claim 2 , wherein in the general formula (1), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0<g≤0.8, and 0<h≤0.5.

4. The silicone skeleton-containing polymer compound according to claim 3 , wherein in the general formula (1), a=0, b=0, c=0, d=0, 0≤e≤0.3, 0≤f≤0.2, 0<g≤0.8, and 0<h≤0.5.

5. The silicone skeleton-containing polymer compound according to claim 2 , wherein in the general formula (1), a=0, b=0, c=0, d=0, 0≤e≤0.3, 0≤f≤0.2, 0<g≤0.8, and 0<h≤0.5.

6. The silicone skeleton-containing polymer compound according to claim 1 , wherein in the general formula (1), 0≤a≤0.5, 0≤b≤0.3, 0≤c≤0.5, 0≤d≤0.3, 0≤e≤0.8, 0≤f≤0.5, 0<g≤0.8, and 0<h≤0.5.

7. The silicone skeleton-containing polymer compound according to claim 6 , wherein in the general formula (1), a=0, b=0, c=0, d=0, 0≤e≤0.3, 0≤f≤0.2, 0<g≤0.8, and 0<h≤0.5.

8. The silicone skeleton-containing polymer compound according to claim 1 , wherein in the general formula (1), a=0, b=0, c=0, d=0, 0≤e≤0.3, 0≤f≤0.2, 0<g≤0.8, and 0<h≤0.5.

9. A method for producing the silicone skeleton-containing polymer compound according to claim 1 , comprising:
introducing a carboxyl group by reacting a part or all of alcoholic or phenolic hydroxyl groups of a silicone skeleton-containing polymer compound having a repeating unit shown by the general formula (7) with a dicarboxylic acid anhydride,

wherein R 1 to R 4 , “a”, “b”, “c”, “d”, “m”, X, Y, and W have the same meanings as defined above; “k” and “l” are each a positive number satisfying k=e+g and l=f+h; and “e”, “f”, “g”, and “h” have the same meanings as defined above,
wherein the silicone skeleton-containing polymer compound shown by the general formula (7) is a polymer compound obtained by polymerization reaction of:
either or both of a hydrogensilphenylene shown by the structural formula (8) and a dihydroorganosiloxane shown by the general formula (9),

wherein R 3 , R 4 , and “m” have the same meanings as defined above;
either or both of a phenol compound having two allyl groups and shown by the general formula (10) and a compound having two allyl groups and shown by the general formula (11),

wherein Z, R 5 , R 6 , “n” and “x” have the same meanings as defined above,

wherein V, R 7 , R 8 , “p” and “y” have the same meanings as defined above; and
a phenol compound having two allyl groups and shown by the general formula (12)

wherein T and R 9 have the same meanings as defined above;
in the presence of a catalyst.

10. The method for producing the silicone skeleton-containing polymer compound according to claim 9 , wherein the phenol compound having two allyl groups and shown by the general formula (12) is a compound shown by the general formula (13),

wherein R 9 has the same meaning as defined above, and “s” is a positive number of 1 to 12.

11. The method for producing the silicone skeleton-containing polymer compound according to claim 9 , wherein the phenol compound having two allyl groups and shown by the general formula (12) is a compound shown by the general formula (14),

wherein R 9 has the same meaning as defined above.

12. A silicone skeleton-containing polymer compound comprising a repeating unit shown by the general formula (24) and having a weight average molecular weight of 3,000 to 500,000,

wherein R 21 to R 24 may be the same or different and represent a monovalent organic group having 1 to 15 carbon atoms and optionally containing an oxygen atom; R 18 and R 19 may be the same or different and represent a monovalent organic group having 1 to 28 carbon atoms and optionally containing an oxygen atom; m′ is an integer of 0 to 100; “o” is an integer of 0 to 100; c′, d′, e′, a

Assignees

• Shinetsu Chemical Co

Inventors

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

Classifications

• G03F7/40

  Treatment after imagewise removal, e.g. baking · CPC title

• G03F7/38

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

• G03F7/168

  Finishing the coated layer, e.g. drying, baking, soaking · CPC title

• C08G77/18

  to alkoxy or aryloxy groups · CPC title

• C08G77/16

  to hydroxy groups · CPC title