Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From fluorine-containing reactant
Reexamination Certificate
1999-12-16
2001-10-02
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From fluorine-containing reactant
C528S176000, C528S272000, C528S332000, C528S397000, C528S422000
Reexamination Certificate
active
06297351
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to polybenzoxazole resins which are excellent in electrical characteristics, thermal characteristics, and mechanical characteristics, and which are usable as layer insulation films and protective films for semiconductors, layer insulation films of multilayer circuits, cover coats of flexible copper-clad sheets, solder resist films, liquid crystal-aligned films, etc.
2. Related Art Statement
Among the characteristics required for insulation materials for semiconductors, electric characteristics, particularly, dielectric constant and heat resistance are most important characteristics. In order to allow these two characteristics to be compatible with each other, organic insulation films of high heat resistance are expected. For example, inorganic insulation films such as silicon dioxide which have hitherto been used, have a high heat resistance, but are high in dielectric constant, and the two characteristics are hardly compatible with each other. Organic insulation films represented by polyimide resins are excellent in electric characteristics and heat resistance and have compatibility in the two characteristics, and are actually used as solder resists, cover layers, liquid crystal-aligned films, and the like.
However, with recent enhancement in function and performance of semiconductors, remarkable improvement of electric characteristics and heat resistance is needed, and resins of further higher performances are demanded. Particularly, those materials are expected which have a low dielectric constant of 3.0 or lower and which have a glass transition point (Tg) of 400° C. or higher. As to polyimide resins, it has been also attempted to attain the above properties, for example, by introducing fluorine and trifluoromethyl group into the high molecules, but at present the properties have not yet reached the desired level.
Among resins other than polyimide resins, polybenzoxazole resins are expected. The presence of two carboxyl groups in the imide ring of polyimide resins adversely affect electric characteristics. In general polybenzoxazole resins are essentially superior to polyimide resins in electric characteristics, and hence it is easy to allow heat resistance and dielectric constant to be compatible with each other. However, the level of electric characteristics required is very high and the conventional polybenzoxazole resins have not reached the required level.
OBJECT AND SUMMARY OF THE INVENTION
The object of the present invention is to solve the above problems and provide resins excellent in electric characteristics and heat resistance.
As a result of intensive research conducted in an attempt to solve the above problems, the inventors have found a polybenzoxazole precursor having recurring units represented by the following general formula (1), and a polybenzoxazole resin having a structure obtained by cyclizing said polybenzoxazole precursor, and have accomplished the present invention.
According to the first embodiment, in the above formula (1), n denotes an integer of 1-1000, X is selected from bivalent aromatic groups represented by the following general formulas (2)-(4) each having two OR groups (Rs each represents H or a monovalent organic group and may be the same or different), the amide group in the formula (1) and said OR group respectively bond to the adjacent carbon atoms of the aromatic group, and Y denotes a bivalent organic group containing fluorine.
In the formulas (2)-(4), R
1
, R
5
and R
11
each denotes F or a monovalent organic group containing fluorine, R
2
, R
6
, R
7
, R
8
, R
12
, R
13
, R
14
, R
15
and R
16
each denotes H, F or a monovalent organic group containing fluorine and may be the same or different, R
3
, R
4
, R
9
, RP
10
, R
17
and R
18
each denotes H or a monovalent organic group and may be the same or different.
According to the second embodiment, in the formula (1), n denotes an integer of 1-1000, Y is selected from bivalent aromatic groups represented by the following general formulas (5)-(7), and X denotes a bivalent aromatic group containing fluorine and having two OR groups (Rs each denotes H or a monovalent organic group and may be the same or different), and the amide group in the formula (1) and the OR group respectively bond to the adjacent carbon atoms of the aromatic group.
In the formulas (5)-(7), R
19
, R
23
and R
29
each denotes F or a monovalent organic group containing fluorine, and R
20
, R
21
, R
22
, R
24
, R
25
, R
26
, R
27
, R
28
, R
30
, R
31
, R
32
, R
33
, R
34
, R
35
and R
36
each denotes H, F or a monovalent organic group containing fluorine and may be the same or different.
DETAILED DESCRIPTION OF THE INVENTION
The polybenzoxazole precursor of the present invention can be obtained from a dicarboxylic acid and a bisaminophenol compound or a diaminodihydroxy compound or a derivative thereof such as an esterification product or an etherification product by acid chloride method, active ester method or condensation reaction method in the presence of a dehydration condensation agent such as polyphosphoric acid or dicyclohexylcarbodiimide.
As examples of diaminodihydroxy compounds used in the present invention and particularly constituting the formula (2), mention may be made of 1,3-diamino-4,6-dihydroxydifluorobenzene, 1,4-diamino-3,6-dihydroxydifluorobenzene, 1,4-diamino-2,3-dihydroxydifluorobenzene, 1,2-diamino-3,6-dihydroxydifluorobenzene, 1-trifluoromethyl-2,4-diamino-3,5-dihydroxybenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxybenzene, 1-trifluoromethyl-2,4-diamino-3,5-dihydroxyfluorobenzene, 1-trifluoromethyl-2,5-diamino-3,6-dihydroxyfluorobenzene, 1,4-bis(trifluoromethyl)-2,5-diamino-3,6-dihydroxybenzene, 1-pentafluoroethyl-2,5-diamino-3,6-dihydroxybenzene, 1-perfluorocyclohexyl-2,5-diamino-3,6-dihydroxybenzene, 1,3-diamino-4,6-diethoxydifluorobenzene, and derivatives thereof such as ester compounds and ether compounds. The diaminodihydroxy compounds are not limited to these examples. These compounds can be used each alone or in combination.
As examples of diaminodihydroxy compounds used in the present invention and particularly constituting the formula (3), mention may be made of 2,7-diamino-3,6-dihydroxytetrafluoronaphthalene, 2,6-diamino-3,7-dihydroxytetrafluoronaphthalene, 1,6-diamino-2,5-dihydroxytetrafluoronaphthalene, 3,6-diamino-2,5-dihydroxytetrafluoronaphthalene, 2,7-diamino-1,8-dihydroxytetrafluoronaphthalene, 1-trifluoromethyl-3,6-diamino-2,7-dihydroxynaphthalene, 1,5-bis(trifluoromethyl)-3,7-diamino-2,6-dihydroxynaphthalene, 1-trifluoromethyl-3,6-diamino-2,5-dihydroxynaphthalene, 1-pentafluoroethyl-3,6-diamino-2,7-dihydroxynaphthalene, 1-perfluorocyclohexyl-3,6-diamino-2,7-dihydroxynaphthalene, 1,5-bis(trifluoromethyl)-3,7-diamino-2,6-dihydroxydifluoronaphthalene, 2,6-diamino-3,7-diethoxytetrafluoronaphthalene, 1,4,5,8-tetra-(trifluoromethyl)-2,7-diamino-3,6-dihydroxynaphthalene, and derivatives thereof such as ester compounds and ether compounds. The diaminodihydroxy compounds are not limited to these examples. These compounds can be used each alone or in combination.
As examples of bisaminophenol compounds used in the present invention and particularly constituting the formula (4), mention may be made of 4,4′-diamino-3,3′-dihydroxy-5,5′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-5,5′-pentafluoroethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-6,6′-trifluoromethylbiphenyl, 4,4′-diamino-3,3′-dihydroxy-6,6′-pentafluoroethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-5,5′-trifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-5,5′-pentafluoroethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6,6′-trifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6,6′-pentafluoroethylbiphenyl, 3,4′-diamino-4,3′-dihydroxy-5,5′-trifluoromethylbiphenyl, 3,4′-diamino-4,3′-dihydroxy-5,5′-pentafluoroethylbiphenyl, 3,4′-diamino-4,3′-dihydro
Egucih Toshimasa
Hatao Takuya
Higashida Nobuhiro
Mizumoto Yoko
Murayama Mitsumoto
Smith , Gambrell & Russell, LLP
Sumitomo Bakelite Company Limited
Truong Duc
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