Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-12-17
2001-03-27
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S259000, C526S270000, C526S281000, C526S916000, C525S256000, C525S267000, C525S289000, C525S283000, C430S270100
Reexamination Certificate
active
06207779
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel ring-opened polymer, and more particularly relates to a novel ring-opened polymer that is prepared by reacting at least one specific pericyclic olefin through ring-opening metathesis polymerization.
2. Description of the Prior Art
Nowadays, thin film coating and photosensitive techniques both play very important roles in chemical engineering technology. A resin suitable for thin film coating should meet the requirements of having good film properties and good adherence to substrates. Therefore, the glass transition temperature of such resin should not be too high. To be considered for application to IC photoresists, a suitable resin should further have other properties such as high etch and heat resistance, properties which are frequently achieved by molecular design.
To date, resins frequently used for thin film coating can be classified into two types. One is an acrylic resin that is synthesized by free radical polymerization, which is disclosed in U.S. Pat. No. 4,491,628. The other type is a pericyclic resin that is synthesized by free radical polymerization, which is disclosed in U.S. Pat. No. 3,928,497. However, acrylic resins have inferior etch resistance, and can not be developed by commercial developer, such as 2.38% TMAH (tetramethylammonium hydroxide). Free radical polymerized pericyclic resins have too crowded a structure, thus resulting in a low freedom and too high a glass transition temperature. Therefore, such a pericyclic resin has inferior film properties and crack will occur when it is coated on substrates.
SUMMARY OF THE INVENTION
Therefore, an object of the present invention is to solve the above-mentioned problems and to provide a novel resin, which has good etch resistance, suitable glass transition temperature, good mechanical properties, good film properties, and can be developed by commercial developers.
To achieve the above object, the present invention provides a novel resin, which is an unsaturated ring-opened polymer and is prepared by reacting at least one pericyclic olefin selected from those represented by formulae (I) and (II) through ring-opening metathesis polymerization (ROMP)
wherein
A and B may be the same or different and are independently selected from the group consisting of halogen, hydrogen, C
3-20
cyclic or pericyclic alkyl, C
1-20
linear and branched alkyl, C
6-20
aryl, C
7-20
arylalkyl, C
7-20
alkylaryl, silyl, alkylsilyl, germyl, alkylgermyl, alkoxycarbonyl, acyl, and a heterocylic group; or, A and B are linked together to form a C
3-20
saturated or unsaturated cyclic hydrocarbon group or a substituted or unsubstituted heterocyclic group;
C is selected from the group consisting of oxygen, sulfur,
—CH
2
—, and —SiH
2
—,
wherein each R
1
is independently selected from C
1-20
alkyl and phenyl;
each R is independently selected from hydrogen, halogen, and C
1-20
alkyl; and
each n is an integer from 1 to 6.
Such an unsaturated ring-opened polymer has vinylene groups on its main chain.
The present invention further provides another ring-opened polymer, which is obtained from subjecting the above unsaturated ring-opened polymer to hydrogenation. Such a hydrogenated ring-opened polymer has ethylene groups on its main chain.
DETAILED DESCRIPTION OF THE INVENTION
According to the present invention, formula (I) or (II) is preferably a norbornene derivative, that is, formula (I) or (II) has n equal to 1 and C equal to O (oxygen). That is to say, the ring-opened polymer is prepared by reacting at least one norbornene derivative selected from those represented by formulae (I) and (II) (n=1, C=O) through ring-opening metathesis polymerization.
When formula (I) is a norbornene derivative, representative examples of formula (I) include
Formula (I) can also be a tricyclic lactone represented by the following formula
wherein m is an integer from 1 to 3, or
wherein q is an integer from 1 to 3, and X is selected from O, N, or S.
According to the above descriptions, the ring-opened polymer of the present invention is prepared by reacting at least one pericyclic olefin selected from those represented by formulae (I) and (II) through ring-opening metathesis polymerization. For example, at least one pericyclic olefin of formula (I) or (II) can be reacted with at least one other cyclic olefin through ring-opening metathesis copolymerization to obtain the ring-opened polymer of the present invention.
Another example is that at least one pericyclic olefin of formula (I) or (II) is reacted with at least one other cyclic olefin and at least one monomer other than cyclic olefins through ring-opening metathesis copolymerization to obtain the ring-opened polymer of the present invention.
A “chemically amplified resist” is a kind of photoresist in which the rate of dissolution in a developer can be changed by an acid produced by photoirradiation. Such a photoresist solution includes a protected resin, a photoacid generator, and a solvent. The so-called protected resin is a resin that is protected by an acid-labile protective group. The resin will be converted into alkali-soluble when the acid-labile protective group is decomposed. When the chemically amplified resist applied on a substrate is exposed to photo, the photoacid generator will generate acid, and the acid will decompose the acid-labile protective group in the resin, thus making the resin soluble in an alkali developer.
Therefore, if the ring-opened polymer of the present invention is used for a chemically amplified resist, such a ring-opened polymer preferably has an acid-labile protective group, which will be decomposed in the presence of an acid so that the ring-opened polymer will be converted into an alkali-soluble polymer.
Such an acid-labile protective group may be present in formula (I), formula (II), the cyclic olefin that can be copolymerized with formula (I) or (II), or present in any monomer that can be copolymerized with formula (I) or (II).
For example, the cyclic olefin that can be copolymerized with formula (I) or (II) can be norbornene or a norbornene derivative. Such a norbornene derivative can have an acid-labile protective group D. Thus, when the ring-opened polymer of the present invention is in the presence of an acid, the protective group D will be hydrolyzed, such that the ring-opened polymer will be converted to an alkali soluble polymer. Such norbornene derivatives include:
wherein
D is an acid-labile protective group, which is decomposed in the presence of an acid, so as to make the ring-opened polymer alkali-soluble, and
each R
3
is independently selected from the group consisting of hydrogen, C
1-20
linear and branched alkyl, C
3-20
cyclic and pericyclic alkyl.
Representative examples of D include:
wherein R
4
is selected from the group consisting of hydrogen, C
1-20
linear and branched alkyl, C
3-20
cyclic and pericyclic alkyl.
A compound of formula (I) can be reacted with a norbornene derivative containing acid-labile protective groups through ROMP to obtain a ring-opened polymer. For example, a compound of formula (I) (when n=1) can be reacted with a compound of formulae (VI) and (VIII) to obtain a ring-opened polymer represented by formula (III), which has vinylene groups on its main chain,
wherein
A and B may be the same or different and are independently selected from the group consisting of halogen, hydrogen, C
3-20
cyclic or pericyclic alkyl, C
1-20
linear and branched alkyl, C
6-20
aryl, C
7-20
arylalkyl, C
7-20
alkylaryl, silyl, alkylsilyl, germyl, alkylgermyl, alkoxycarbonyl, acyl, and a heterocylic group; or, A and B are linked together to form a C
3-20
saturated or unsaturated cyclic hydrocarbon group or a substituted or unsubstituted heterocyclic group;
C is selected from the group consisting of oxygen, sulfur,
—CH
2
—, and —SiH
2
—,
wherein each R
1
is independently selected from C
1-20
alkyl and phenyl;
each R is independently selected from hydrogen, halogen, and C
1-20
alkyl;
D is an acid-labile prote
Chang Jui-Fa
Chang Sheng-Yueh
Chen Jian-Hong
Ho Bang-Chein
Yeh Tai-Sheng
Darby & Darby
Harlan R.
Industrial Technology Research Institute
Wu David W.
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