Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
1996-11-26
2003-12-16
Weiner, Laura (Department: 1745)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
Reexamination Certificate
active
06664021
ABSTRACT:
BACKGROUND OF THE INVENTION
(i) Field of the Invention
The present invention relates to a photosensitive resin composition. More specifically, it relates to a negative type photosensitive resin composition having excellent sensitivity and resolving properties which can inhibit volume shrinkage at the time of curing, can suitably adhere to a substrate, and can form a polyimide coating film pattern having good heat resistance on the substrate by baking.
(ii) Description of the Related Art
Photosensitive polyimides which are heat-resistant photosensitive materials have been widely used as insulating films and passivation films for semiconductors. The well known. photosensitive polyimides can be prepared by mixing a polyimide precursor with a compound having a carbon-carbon double bond capable of polymerizing by light irradiation, or chemically bonding the above-mentioned compound to the above-mentioned precursor by an ester linkage. For example, they are disclosed in Japanese Patent Application Laid-open Nos. (Sho)54-145794 and (Hei)2-144539, and Japanese Patent Publication No. (Sho)55-41422. However, in all of these polyimides, it is necessary to introduce a large amount, 50% by weight or more, of-the compound having the carbon-carbon double bond into the polyimide precursor in order to practically carry out patterning, so that deterioration of resolving properties and large volume shrinkage at curing cannot be avoided. On the other hand, there has also been suggested a method in which instead of the compound having a carbon-carbon double bond, a compound for generating an acid by light irradiation is used, whereby the above-mentioned problems can be solved. For example, Japanese Patent Application Laid-open No. 3-763 discloses a method which comprises blending the compound for generating an acid by light irradiation with a polyimide having an acyloxy group, and Japanese Patent Application Laid-open No. 4-120171 discloses a method which comprises blending the above-mentioned compound with a polyamic acid derivative into which an organic group is introduced by an ester linkage, whereby the formation of a positive type pattern can be achieved. These compositions obtained by these methods have excellent sensitivity and can inhibit the volume shrinkage at the time of curing, but the adhesion of them to the substrate is so poor that they are not practical.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a negative type photosensitive resin composition having excellent sensitivity and resolving properties which inhibits volume shrinkage at the time of curing, possesses good adhesion to a substrate and can be baked.
The present inventors have intensively conducted investigation with the intention of solving the above-mentioned problems of known techniques, and as a result, they have found that these problems can be solved by a composition comprising a specific polyimide precursor whose molecular terminal has been reacted with an aminosilicon compound having a hydrolytic alkoxy group bonded to a silicon atom, and a compound for generating an acid with the aid of light. In consequence, the present invention has now been completed.
(1) A photosensitive resin composition of the present invention is characterized by a compound for generating an acid by light irradiation and at least one polyimide precursor selected from the group consisting of; (a) a silicon-containing polyimide precursor obtained from A mols of a tetracarboxylic dianhydride or its derivative formed by adding 2 mols or less of a monovalent saturated alcohol to 1 mol of the tetracarboxylic dianhydride, B mol of a diamine and C mols of an aminosilicon compound represented by the formula (1)
H
2
N—R
1
—SiR
2
3−k
X
k
(1)
{wherein R
1
is —(CH
2
)
s
—,
(wherein s is an integer of from 1 to 4); R
2
is independently an alkyl group having 1 to 6 carbon atoms, a phenyl group or a phenyl group substituted by an alkyl group having 7 to 12 carbon atoms; X is a hydrolytic alkoxy group; and k is 1≦k≦3}
in a ratio meeting the following formulae (2) and (3)
1
≦
C
A
-
B
≦
2.5
(
2
)
0.1
≦
C
B
+
C
≦
1
,
(
3
)
(b) a silicon-containing polyamic acid ester obtained by esterifying the precursor (a) with a monovalent saturated alcohol, and (c) partially esterified silicon-containing polyamic acid ester obtained by partially esterifying the precursor (a) with the monovalent saturated alcohol.
As further preferable embodiments,
(2) the photosensitive resin composition described in the preceding paragraph (1) wherein the silicon-containing polyimide precursor (a) is a silicon-containing polyamic acid.
(3) The photosensitive resin composition described in the preceding paragraph (1) wherein the silicon-containing polyimide precursor (a) is a polyamic acid ester.
(4) The photosensitive resin composition described in the preceding paragraph (1) wherein the polyimide precursor is the silicon-containing polyamic acid ester (b).
(5) The photosensitive resin composition described in the preceding paragraph (1) wherein the silicon-containing polyimide precursor (a) is a partially esterified polyamic acid ester.
(6) The photosensitive resin composition described in the preceding paragraph (1) wherein the polyimide precursor is the partially esterified silicon-containing polyamic acid ester (c).
(7) The photosensitive resin composition described in the preceding paragraph (1) wherein the partially esterified silicon-containing polyamic acid ester (c) is the partially esterified silicon-containing polyamic acid ester (c) which is partially imidated as much as less than 40%.
(8) The photosensitive resin composition described in the preceding paragraph (1) wherein the monovalent saturated alcohol is a monovalent saturated alcohol having 1 to 7 carbon atoms.
(9) The photosensitive resin composition described in the preceding paragraph (1) wherein X of the aminosilicon compound represented by the formula (1) is an alkoxyl group having 1 to 4 carbon atoms, and R
1
is a phenylene group or a trimethylene group.
(10) The photosensitive resin composition described in the preceding paragraph (1) wherein the tetracarboxylic dianhydride is represented by the formula (4)
the diamine is represented by the formula (5)
H
2
N—R
5
—NH
2
(5)
the main chain of the polyimide precursor comprises e mols, f mols, n mols, m mols, h mols and i mols (each of e, f, n, m, h and i is 0 or a positive integer) of constitutional units represented by the formulae (6), (7), (8), (9), (10) and (11), respectively,
and e, f, n, m, h and i meet the equation (12)
0
≦
100
×
m
+
h
+
2
i
2
(
e
+
f
+
n
+
m
+
h
+
i
)
<
40
(
12
)
(each R
3
is independently a tetravalent carbocyclic aromatic group, a heterocyclic group, an alicyclic group or an aliphatic group; each R
5
is independently a divalent aliphatic group having 2 or more carbon atoms, an alicyclic group, an aromatic aliphatic group, a carbon cyclic aromatic group, a heterocyclic group or a polysiloxane group; and R
6
is an alkyl group having 1 to 7 carbon atoms).
(11) The photosensitive resin composition described in the preceding paragraph (1) wherein the amount of the compound for generating an acid by light irradiation is in the range of from 0.5 to 15 parts by weight based on 100 parts by weight of the polyimide precursor.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENT
The polyimide precursor which can be used in the photosensitive resin composition of the present invention is a specific silicon-containing polyimide precursor, a silicon-containing polyamic acid, a silicon-containing polyamic acid ester or a partially esterified silicon-containing polyamic acid.
The polyimide precursor which can be used in the photosensitive resin composition of the present invention can be obtained by carrying out a reaction for forming an amide bond between molecules of a tetracarboxylic dianhydride, its derivative formed by adding a monovalent saturated alcohol to the tetracarboxylic dianhydr
Katou Kouichi
Kunimune Kouichi
Maeda Hirotoshi
Watanabe Eiji
Chisso Corporation
Leydig , Voit & Mayer, Ltd.
Weiner Laura
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