Developer for photosensitive polyimide resin composition

• US 6,403,289 B1
• Filed: 10/30/1998
• Issued: 06/11/2002
• Est. Priority Date: 10/31/1997
• Status: Expired due to Fees

• Current Assignee: Nippon Zeon Co., Ltd. (BASF SE), Fujitsu Limited
• Original Assignee: Nippon Zeon Co., Ltd. (BASF SE), Fujitsu Limited
• Inventors: Tanaka, Akira, Yoneda, Yasuhiro, Sakamoto, Kei, Yokouchi, Kishio
• Primary Examiner(s): Huff, Mark F.
• Assistant Examiner(s): BARRECA, NICOLE M
• Application Number:
  US09/183,341
• Time in Patent Office: 1,320 Days
• Field of Search: 430/322, 430/325, 430/329, 430/331
• US Class Current: 430/329
• CPC Class Codes: G03F 7/037 the binders being polyamides or polyimides
• CPC Class Codes: G03F 7/322 Aqueous alkaline compositions

Abstract

The invention relates to a developer for photosensitive polyimide resin compositions, comprising an alkaline aqueous solution containing a basic compound (A) represented by a formula (1):

wherein X⁺ is N⁺ or P⁺, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 ring forming carbon atoms, Y⁻ is a monovalent anion, m is 0 or 1, n is 3 or 4, and m+n is 4, with the proviso that when m is 0, n is 4, and R is an alkyl group, the total number of carbon atoms of 4 alkyl groups is at least 13, or when m is 1, n is 3, and R is an alkyl group, the total number of carbon atoms of 3 alkyl groups is at least 6.

Claims

1. A developer for photosensitive polyimide resin compositions, which is suitable for use in development after patterning exposure of a photosensitive layer formed from a photosensitive polyimide resin composition containing a polyamic acid having at least one photopolymerizable functional group in its molecular chain, the developer comprising an alkaline aqueous solution containing a basic compound (A) represented by formula (1):

wherein X⁺ is N⁺ or P⁺, R is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 10 ring forming carbon atoms, Y⁻

is a monovalent anion, m is 0 or 1, n is 3 or 4 and m+n is 4, with the proviso. that when m is 0, n is 4, and R is an alkyl group, the total number of carbon atoms of the 4 alkyl groups is at least 13, or when m is, 1, n is 3, and R is an alkyl group, the total number of carbon atoms of the 3 alkyl groups is at least 6, and wherein the basic compound (A) is a benzyltrialkylammonium salt, a benzyltriarylammonium salt, a tetraalkylphosphonium salt, a benzyltrialkylphosphonium salt or a benzyltriarylphosphonium salt, and at least one basic compound (B) selected from the group consisting of tetraalkylammonium salts in which the 4 alkyl groups have not greater than 12 total carbon atoms, choline, tertiary aliphatic amines in which the number of carbon atoms of each aliphatic group is from 1 to 5, pyridine and derivatives thereof, the basic compounds being in a molar ratio (A;

B) ranging from 5;

95 to 90;

10, and the alkaline aqueous solution having a pH of at least 10.0.

2. The developer according to claim 1, wherein the basic compound (A) represented by the formula (1) contains, OH⁻

, or a halide anion selected from Cl⁻

, Br⁻

, F⁻

or I⁻

as the monovalent anion Y⁻

.

3. The developer according to claim 1, wherein the benzyltrialkylammonium salt is a compound represented by a formula (4):

wherein R₁ is an alkyl group having 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms of the 3 alkyl groups is at least 6, the 3 alkyl groups may be the same or different from one another, and Y⁻

is a monovalent anion.

4. The developer according to claim 1, wherein the benzyltriarylammonium salt is a compound represented by a formula (5):

wherein Ar is an aryl group having 6 to 10 ring forming carbon atoms, and Y⁻

is a monovalent anion.

5. The developer according to claim 1, wherein the tetraalkylphosphonium salt is a compound represented by a formula (6):

6. The developer according to claim 1, wherein the benzyltrialkylphosphonium salt is a compound represented by a formula (7):

wherein R₁ is an alkyl group having 1 to 20 carbon atoms, with the proviso that the total number of carbon atoms of the 3 alkyl groups is at least 6, the 3 alkyl groups may be the same or different from one another, and Y⁻

is a monovalent anion.

7. The developer according to claim 1, wherein the benzyltriarylphosphonium salt is a compound represented by a formula (8):

wherein Ar is an aryl group having 6 to 10 ring forming carbon atoms, and Y⁻

is a monovalent anion.

8. The developer according to claim 1, wherein the basic compound (A) represented by the formula (1) is benzyltriethylammonium hydroxide, benzyltriphenylammonium hydroxide, tetrabutylphosphonium hydroxide or benzyltriethylphosphonium hydroxide.

9. The developer according to claim 1, wherein a medium of the alkaline aqueous solution comprises at least 51 wt. % of water and at most 49 wt. % of at least one component selected from the group consisting of organic solvents and surfactants.

10. The developer according to claim 9, wherein the organic solvent is at least one oxygen-containing compound selected from the group consisting of monohydric alcohols, polyhydric alcohols, ketones and esters.

11. The developer according to claim 9, wherein the medium of the alkaline aqueous solution comprises water and 1 to 40 wt. % of the organic solvent.

12. The developer according to claim 9, wherein the medium of the alkaline aqueous solution comprises water, 1 to 40 wt. % of the organic solvent and 0.01 to 1 wt. % of the surfactant.

13. The developer according to claim 1, wherein the polyamic acid is a polyamic acid having, in its main chain, repeating units represented by a formula (9):

wherein R¹ is a tetravalent organic group, and R² is a bivalent organic group, and at both terminals thereof, at least one actinic ray-sensitive functional group selected from the group consisting of a group Z¹ represented by a formula (10);

wherein X is a single bond, —

O—

, —

CO—

, —

COO—

, —

OCO—

, —

OCOO—

, —

COCH₂O—

, —

S—

, —

SO—

, —

SO₂—

or —

SO₂—

, R³, R⁴, R⁵, R⁶ and R⁷ are independently a substituent group having a photopolymerizable carbon-carbon double bond, m is 0 or 1, and n is an integer within a range of from 1 to 3, and a group Z² represented by a formula (11);

wherein R³, R⁴, R⁵, R⁶ and R⁷ are independently a substituent group having a photopolymerizable carbon-carbon double bond, and m is 0 or 1.

14. The developer according to claim 1, wherein the photosensitive polyimide resin composition comprises the polyamic acid, a photosensitive auxiliary, a photopolymerization initiator and a solvent in an amount sufficient to uniformly dissolve the individual components.

15. The developer according to claim 14, wherein the photosensitive polyimide resin composition further comprises at least one of 1H-tetrazoles.

16. A pattern forming process comprising the steps of forming a photosensitive layer on a substrate with a photosensitive resin composition comprising a polyamic acid, subjecting the photosensitive layer to patterning exposure, and then developing the thus-exposed photosensitive layer using the developer of claim 1.

17. A pattern forming process according to claim 16, wherein the alkaline aqueous solution has a pH in the range of from 10.0 to 13.8.

18. A pattern forming process according to claim 16, wherein the alkaline aqueous solution has a pH in the range of from 11.0 to 13.0.

19. The developer according to claim 1, further comprising 1 to 40 wt. % of an organic solvent.

20. The developer according to claim 19, wherein the alkaline aqueous solution has a pH in the range of from 10.0 to 13.8.

21. The developer according to claim 19, wherein the alkaline aqueous solution has a pH in the range of from 11.0 to 13.0.

22. The developer according to claim 1, wherein the alkaline aqueous solution has a pH in the range of from 10.0 to 13.8.

23. The developer according to claim 1, wherein the alkaline aqueous solution has a pH in the range of from 11.0 to 13.0.