Radiation imagery chemistry: process – composition – or product th – Diazo reproduction – process – composition – or product – Composition or product which contains radiation sensitive...
Reexamination Certificate
2001-01-29
2003-02-25
Chu, John S. (Department: 1752)
Radiation imagery chemistry: process, composition, or product th
Diazo reproduction, process, composition, or product
Composition or product which contains radiation sensitive...
C430S165000, C430S192000, C430S193000, C430S326000, C430S330000
Reexamination Certificate
active
06524764
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a positive type photosensitive polyimide precursor composition where regions exposed using ultraviolet radiation dissolve in aqueous alkali solution and which is suitable for semiconductor element surface protective films, layer insulation films and the like. That is to say, it relates to a positive type photosensitive polyimide precursor composition suitable for semiconductor element surface protective films, layer insulation films and the like, where regions exposed using ultraviolet radiation dissolve in aqueous alkali solution.
TECHNICAL BACKGROUND
As examples of positive type heat-resistant resin precursor compositions where the exposed regions are dissolved by developing, there are known those where a naphthoquinone diazide is added to a polyamic acid (JP-A-52-13315), those where a naphthoquinone diazide is added to a soluble polyimide which possesses hydroxyl groups (JP-A-64-60630) and those where a naphthoquinone diazide is added to a polyamide which possesses hydroxyl groups (JP-A-56-27140).
However, where a naphthoquinone diazide is added to an ordinary polyamic acid there is the problem that, since the solubility of the polyamic acid carboxyl groups is higher than the inhibitory effect of the naphthoquinone diazide in terms of alkali solubility, in most cases the desired pattern cannot be obtained. Furthermore, where a hydroxyl group-containing soluble polyimide resin is added, although there is little such aforesaid problem, there is the difficulty that, in order to provide solubility, the structures are limited and the solvent resistance of the polyimide resin obtained is poor.
Taking into account the aforesaid shortcomings, in the present invention it has been discovered that by adding a novel naphthoquinone diazide compound of specified structure to a polyimide precursor, the resin composition obtained essentially does not dissolve at all in alkali developer prior to exposure but, once exposed, it readily dissolves in the alkali developer, so there is little film loss due to the developing and developing is possible in a short time. It is on this discovery that the present invention is based.
That is to say, in accordance with the present invention, by adding a specified naphthoquinone diazide compound to a polyimide precursor of specified structure, there can be provided a positive type heat-resistant resin composition which shows little film loss in the unexposed regions due to developing and, furthermore, which can be developed in a short time.
DISCLOSURE OF THE INVENTION
The present invention relates to a positive type photosensitive resin precursor composition which is characterized in that it contains polymer having, as its chief component, structural units represented by the following general formula (1) and, furthermore, in that it satisfies the following conditions (a) and/or (b).
(a) There is included an ester of a naphthoquinone diazide sulphonic acid and a phenol compound of dipole moment 0.1 to 1.6 debye
(b) There is included a phenol compound represented by general formula (8) and a naphthoquinone diazide sulphonic acid and/or an ester of a phenol compound represented by general formula (8) and a naphthoquinone diazide sulphonic acid
(In general formula (1), R
1
represents a bivalent to octavalent organic group with at least two carbon atoms, R
2
represents a bivalent to hexavalent organic group with at least two carbon atoms, and R
3
represents hydrogen or an organic group with from one to ten carbons. n is an integer in the range 10 to 100,000, m is an integer in the range 0 to 2, and p and q are integers in the range 0 to 4. However, p and q are not simultaneously 0.)
(In the formula, R
10
, R
11
, R
13
and R
14
each represents a hydrogen atom or a C
1-8
alkyl group, alkoxy group, carboxyl group or ester group. R
12
represents a hydroxyl group, hydrogen atom or C
1-8
alkyl group. &agr;, &bgr;
o
and &dgr; represent integers in the range 0 to 3. However, &agr;+&bgr;≦5, &bgr;+&dgr;≧5 and &agr;+&bgr;>0. x represents an integer in the range 1 to 3.)
Optimum Form for Practising the Invention
In the present invention, the polymer having, as its chief component, structural units represented by general formula (1) is a polymer from which there can be formed, by heating or by means of a suitable catalyst, polymer having imide rings, oxazole rings or other cyclic structures. By forming cyclic structures, the heat resistance and solvent resistance are markedly raised.
Aforesaid general formula (1) represents a hydroxyl group-containing polyamic acid or a polyhydroxyamide and, due to the presence of the hydroxyl groups, the solubility in aqueous alkali solution is better than that of a polyamic acid which does not possess hydroxyl groups. In particular, phenolic hydroxyl groups are the preferred hydroxyl groups in terms of the solubility in aqueous alkali solution. Moreover, by having at least 10 wt % of fluorine atoms in general formula (1), a suitable degree of water repellency is shown at the film interface at the time of the developing with aqueous alkali solution, so permeation at the interface, etc, is suppressed. However, if the fluorine atom content exceeds 20 wt %, the solubility in the aqueous alkali solution is lowered, the organic solvent resistance of the polymer which has been provided with cyclic structures by heat treatment is reduced, and the solubility in fuming nitric acid declines, so this is undesirable. Thus, a fluorine atom content of 10 wt % to 20 wt % is preferred.
In the case where m is 0, hydroxyphthalic acid, bis(hydroxycarboxyphenyl)hexafluoropropane or oxydi(hydroxycarboxybenzene), etc, may be used.
In aforesaid general formula (1), R
1
(OH)
p
(COOR
3
)
m
denotes the acid structural component and it is preferred that this group be a bivalent to octavalent group with at least two carbons, which contains an aromatic ring and possesses from 1 to 4 hydroxyl groups.
Specifically, a group having a structure as represented by general formula (2) is preferred. In this case, R
4
and R
6
represent C
2-20
trivalent or tetravalent organic groups. In particular, groups containing an aromatic ring are preferred in terms of the heat resistance of the polymer obtained, with particularly preferred examples thereof being the trimellitic acid residue, the trimesic acid residue and the naphthalene tricarboxylic acid residue.
R
5
is preferably a hydroxyl group-containing C
3-20
trivalent to hexavalent organic group. In addition, it is preferred that the hydroxyl groups be positioned adjacent to an amide bond. Examples thereof are groups with bonded amino groups such as the bis(3-amino-4-hydroxyphenyl)hexafluoropropane residue and the bis(3-hydroxy-4-aminophenyl)hexafluoropropane residue, which contain fluorine atoms, and the bis(3-amino-4-hydroxyphenyl)propane residue, the bis(3-hydroxy-4-aminophenyl)propane residue, the 3,3′-diamino-4,4′-dihydroxybiphenyl residue, the 3,3′-diamino-4,4′-dihydroxybiphenyl residue, the 2,4-diaminophenol residue, the 2,5-diaminophenol residue and the 1,4-diamino-2,5-dihydroxybenzene residue, which do not contain fluorine atoms.
R
7
and R
8
in general formula (2) may each be hydrogen or a C
1-10
organic group. If there are more than 10 carbons, the solubility in the alkali developer is lowered. R
7
and R
8
may be the same or different. o and s denote 1 or 2, and r denotes an integer in the range 1 to 4. If r is 5 or more, then the properties of the heat-resistant film obtained decline and the water absorption becomes considerable.
Amongst the compounds of general formula (2), those of structure as shown below may be given as preferred examples, but there is no restriction thereto.
In the case where q in the R
2
(OH)
q
moiety of general formula (1) is 1 or more, there can employed a dicarboxylic acid residue, tetracarboxylic acid residue or tricarboxylic acid residue which does not contain hydroxyl groups. As examples thereof, there are the isophthalic acid residue, terephthalic acid residue, dicarbo
Fujita Yoji
Suwa Mitsuhito
Tomikawa Masao
Chu John S.
Morrison & Foerster / LLP
Toray Industries Inc.
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