Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Reexamination Certificate
2001-03-12
2003-03-11
Barts, Samuel (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
C564S426000, C546S081000, C546S088000, C562S452000
Reexamination Certificate
active
06531632
ABSTRACT:
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
The invention relates to novel bis-o-aminophenols and o-aminophenolcarboxylic acids and to a method for their preparation.
Bis-o-aminophenols and o-aminophenolcarboxylic acids are needed in particular for the preparation of high-temperature-stable polymers such as polybenzoxazoles (PBO) and intermediates for their preparation, and for the preparation of hydroxypolyimides (see, for example, European Patent EP 0 264 678 and European Patent EP 0 300 326). PBO intermediates can be prepared in a way such that a dicarboxylic acid chloride is reacted with a bis-o-aminophenol. Whereas, however, numerous dicarboxylic acids and their acid chlorides are available as a result of the diversity of their industrial uses, there are comparatively few bis-o-aminophenols. Moreover, the kind of aminophenol used exerts a considerable influence on the spectrum of properties of the polymer prepared from it. Thus not only the thermal, electrical and mechanical behavior, but also the solubility, stability towards hydrolysis and many other characteristics of the polymer are strongly influenced by the aminophenol used in the preparation.
PBO intermediates can be structured directly at reasonable cost in the form of a photosensitive compound, i.e. without an auxiliary resist. In comparison with other directly photostructurable dielectrics such as polyimide (PI) and benzocyclobutene (BCB), PBO intermediates have the advantage of positive structurability and aqueous alkaline development (see European Patent EP 0 023 662 and European Patent EP 0 264 678). For this purpose the PBO intermediates used must be largely transparent at the exposure wavelength and sufficiently soluble in—preferably metal ion-free—developers. As is the case for the polyimides, polybenzoxazoles also have the great advantage that—in comparison with the cyclized final products—they can be applied to the substrate as readily soluble intermediates and then cyclized on the substrate itself, whereby the solubility and therefore the sensitivity towards solvents and other process chemicals strongly decreases.
Good electrical, mechanical and thermal characteristics are necessary for the use of polybenzoxazoles in microelectronics, in particular as a dielectric between two metal layers, e.g. in multi-chip modules and memory and logic chips, or as a buffer coat between the chip and its outline. When using polymers of the above kind as a dielectric between metallic printed conductors it is very important that the metal not diffuse through the dielectric at high temperature, i.e. at temperatures greater than 300° C. But many metals, especially aluminum, which is currently the most commonly used metal, do diffuse through the dielectric at high temperatures. For this reason the metal is coated with a barrier layer, for example of titanium nitride or a combination of titanium and titanium nitride, which prevents the diffusion of the metal into the dielectric. The use of an additional layer, however, adds significantly to the costs and also requires more time.
Up to now there has been a lack of suitable bis-o-aminophenols and o-aminophenolcarboxylic acids for the preparation of polymers able to meet the strongly increased requirements of the microelectronics sector. Comparable monomers are known, for example, from European Patent Application EP 0 110 420, European Patent Application EP 0 317 942, European Patent Application EP 0 905 123 and European Patent Application EP 0 906 903. But there is no information on the diffusion of metals in the polymers prepared from these after cylization on a substrate (see: European Patent EP 0 264 678 and European Patent Application EP 0 317 942).
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide bis-o-aminophenols and o-aminophenolcarboxylic acids and a method for preparing the same, which overcome the hereinafore-mentioned disadvantages of the heretofore-known compounds and methods of this general type and which are suitable for the preparation of polymers that meet the strongly increased requirements of microelectronics. In particular, these monomers are intended to enable the preparation of readily soluble polymer intermediates which after cyclization on a substrate produce polybenzoxazoles with high temperature stability and, above all, with significantly reduced metal diffusion.
With the foregoing and other objects in view there is provided, in accordance with the invention, bis-o-aminophenols and o-aminophenolcarboxylic acids having structures represented by the respective formulas:
wherein
each of A
1
to A
7
is a univalent ring substituent independently selected from the group consisting of H, F, CH
3
, CF
3
, OCH
3
and OCF
3
;
T is a bivalent polycyclic linking member selected from the group consisting of
wherein independently at each occurrence Q is selected from the group consisting of C—H, C—F, C—CH
3
, C—CF
3
, C—OCH
3
, C—OCF
3
or N, provided that at least one Q signifies N and a maximum of two N atoms may be present in a single ring,
wherein each of A
8
to A
21
is a univalent ring substituent independently selected from the group consisting of H, F, CH
3
, CF
3
, OCH
3
and OCF
3
;
wherein X signifies CH
2
, CF
2
, C(CH
3
)
2
, C(CF
3
)
2
, C(OCH
3
)
2
, C(OCF
3
)
2
, C(CH
3
) (C
6
H
5
), C(C
6
H
5
)
2
, O, N—H, N—CH
3
or N—C
6
H
5
;
wherein
independently at each occurrence Q′ is selected from the group consisting of C—H, C—F, C—CH
3
, C—CF
3
, C—OCH
3
, C—OCF
3
or N,
and M is a bivalent linking member selected from the group consisting of
wherein Q and Q′ are as defined above.
The designations “A
1
-A
3
”, “A
4
-A
7
”, “A
8
-A
10
”, “A
11
-A
14
”, “A
15
-A
17
” and “A
18
-A
21
” in the structural formulae mean that the phenyl groups or cyclic structures carry respectively the residues A
1
, A
2
and A
3
, or A
4
, A
5
, A
6
and A
7
, or A
8
, A
9
and A
10
, or A
11
, A
12
, A
13
and A
14
, or A
15
, A
16
and A
17
, or A
18
, A
19
, A
20
and A
21
.
With the objects of zhe invention in view, there are also provided novel o-nitrophenyl ether compounds from which the bis(o-aminophenols) and o-aminophenolcarboxylic acids of the invention can be prepared by a sequence of reactions as detailed below. The o-nitrophenyl ether compounds of the invention are represented by the formula
wherein A
1
-A
3
and T are defined as above, R is a residue selected from the group consisting of alkyl, alkoxyalkyl, alkenyl, alkoxyalkenyl, alkynyl and alkoxyalkynyl residues with a maximum of 6 C atoms in each case, and phenyl, phenacyl C
6
H
5
CO—CH
2
—, benzyl, benzylalkyl, benzylalkenyl, benzyloxyalkyl, benzyloxyalkenyl, benzylalkoxyalkyl and benzylalkoxyalkenyl residues with a maximum of 4 aliphatic C atoms in each, case, and Y is selected from the group consisting of
and H.
The bis(o-aminophenols) and o-aminophenolcarboxylic acids of the invention are advantageously prepared by a simple synthesis utilizing novel o-nitrophenyl ether compounds of the invention as starting materials, that can be carried out with high reproducibility. Compared to known bis-o-aminophenols and o-aminophenolcarboxylic acids having different T groups, the reactivity of the compounds of the invention with a carboxylic acid derivative such as an acid chloride is unexpectedly modulated so as to increase the selectivity of reaction at the amino group and thus favoring the conversion of the compounds of the invention to polymer intermediates in high yield and purity.
In these novel compounds, the special structure is clearly responsible for the unexpectedly good barrier effect which the polymer intermediates prepared from them exert against metal diffusion. Dielectrics prepared from these kinds of polybenzoxazole intermediates show in particular a significant reduction in aluminum diffusion. This removes the need for an additional barrier layer.
With the objects of the invention in view, there is also provided a process for preparing the respective bis(o-aminophenols) and o-aminophenolcarboxylic acids.
The method used to prepare t
Haussmann Jörg
Maier Gerhard
Sezi Recai
Barts Samuel
Infineon - Technologies AG
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