Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2001-10-02
2003-10-28
Wilson, D. R. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S340000, C525S342000, C428S428000, C428S446000
Reexamination Certificate
active
06639021
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a composition comprising an addition copolymer of cyclic olefins having an alkoxysilyl functional group, a cross-linked material made from the composition, and a film, sheet, or coating made from the composition.
More particularly, the present invention relates to a composition comprising an addition copolymer of cyclic olefins having an alkoxysilyl functional group exhibiting excellent optical transparency, solvent resistance, dimensional stability, heat resistance, and adhesion to metals and inorganic materials, and suitable for use in optical transparent materials and electronic material parts, to a cross-linked product obtained by crosslinking the composition via siloxane bonds, and to a film, sheet, or coating made from the composition.
2. Description of the Background Art
In recent years, to respond to the requirements for lightening, miniaturization, and high integration of optical parts and liquid crystal display elements, substitution of transparent optical resins for inorganic glass in the field of these parts is ongoing. For this reason, further improvement in heat resistance, chemical resistance, dimensional stability, glueing, and adhesion, in addition to optical transparency of resin materials is desired.
Ring-opening polymers of cyclic olefin compounds and their hydrogenated compounds have conventionally been known as materials exhibiting excellent transparency. Many such polymers, however, are inadequate as a glass substitute because of poor heat resistance due to a low glass transition temperature of 200° C. or less.
On the other hand, addition copolymers of norbornene compound disclosed by Japanese Patent Applications Laid-open No. 4-63807 and No. 8-198919, Published Japanese translation of PCT Applications No. 9-508649 and No. 11-505880 have a glass transition temperature of above 200° C. and exhibit superior transparency.
However, these addition (co)polymers are not only difficult to cross-link because of the absence of cross-linking points, but also exhibit inferior dimensional stability, solvent resistance, and chemical resistance.
Japanese Patent Application Laid-open No. 2001-98026 discloses a method of introducing functional groups such as a hydroxyl group to a polymer as a cross-linking point and cross-linking the polymer using a polyfunctional crosslinking agent such as a dicarboxylic acid, e.g. maleic acid, or epoxy resin. However, improvement in the dimensional stability, solvent resistance, and chemical resistance of the resulting cross-linking film obtained using this method is insufficient. To improve these properties, polymer molecules must be directly cross-linked via functional groups introduced in the polymer molecules, without using a cross-linking agent.
One specific method is to introduce unsaturated double bonds to the polymer molecules and cross-link the polymer using a peroxide. However, no sufficient degree of cross-linking can be achieved nor can a product with improved resistance to oxidative degradation be obtained by using this method because of the reaction of the peroxide with an antioxidant which is added to prevent degradation of the polymer by oxidation. A method of irradiating UV lights to cross-link the unsaturated double bonds without using a peroxide may be employed. However, if exposed to strong UV lights with an intension of achieving a high degree of cross-linking, the polymer may be oxidized and become yellow, resulting in impaired transparency.
A method of introducing an alkoxysilyl functional group in the polymer and cross-linking the polymer via siloxane bonds by hydrolysis and condensation can reduce the effect of an antioxidant added to the polymer.
U.S. Pat. No. 5,912,313 discloses a cross-linked polymer with improved solvent resistance obtained by heating an addition (co)polymer of norbornene containing an alkoxysilyl functional group at 300° C. A problem with this technique is degradation of the polymer due to oxidation which occurs when the polymer is heated at 300° C. in oxygen.
WO 98/20394 discloses a composition comprising a norbornene addition copolymer which contains an alkoxysilyl functional group and a photo acid generator (photoinitiator), and a method of forming a cross-linked polymer by irradiating the spin-coated thin film of the composition with UV lights. Irradiation with strong UV lights, however, may change the color of the polymer to yellow. In addition, it is difficult to homogeneously cross-link the polymer over the entire film or sheet which is thicker than a thin film made by spin-coating. Moreover, when the composition contains a photo acid generator, specific cross-linking conditions must be satisfied in which UV rays are blocked to prevent any problems due to cross-linking during storage of the composition or the manufacture of a film or sheet. A more convenient cross-linking method has therefore been desired.
In addition to these problems, cross-linking of a polymer accompanies various changes in the polymer properties such as an increase in the solvent resistance and a decrease in the coefficient of linear expansion (or an increase of dimensional stability), which are not dealt with by U.S. Pat. No. 5,912,313 nor W098/20394.
The present invention has been achieved to solve the above problems and has an objective of providing a composition comprising an addition copolymer of cyclic olefins having an alkoxysilyl functional group exhibiting excellent optical transparency, solvent resistance, dimensional stability, heat resistance, and adhesion to metals and inorganic materials, and being suitable for use in optical transparent materials and electronic material parts, a cross-linked product obtained by cross-linking the composition via siloxane bonds, a method of manufacturing the cross-linked material which is substantially free from degradation by oxidation, a method of manufacturing a cross-linked material by cross-linking this composition by siloxane bonds and a cross-linked material substantially free from deterioration by oxidation, a film or sheet comprising the composition or cross-linked material, a coating agent comprising the composition, and a coating film comprising the cross-linked material.
As a result of extensive studies, the inventors of the present invention found that the problems due to cross-linking during storage of the composition or manufacture of a film or a sheet can be prevented by using the composition of the present invention without employing specific cross-linking conditions in which UV rays are blocked, and that a cross-linked material which is substantially free from degradation by oxidation can be manufactured by heating the composition at 50° C. or more, optionally by causing water or steam at 50° C. or more to come contact with the composition.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides a composition comprising:
an addition copolymer of cyclic olefins which contains a recurring unit (a) shown by the following formula (1),
wherein A
1
to A
4
individually represent a hydrogen atom, a hydrocarbon group having 1-20 carbon atoms, or an alkoxysilyl group or aryloxysilyl group represented by the formula —(CR
1
R
2
)
f
Si(OR
3
)
g
R
4
(3-g)
, —(CR
1
R
2
)
f
Si(R
3
R
4
)OSi(OR
3
)
g
R
4
(3-g)
, or —(CR
1
R
2
)
f
C(O)O(CH
2
)
h
Si(OR
3
)
g
R
4
(3-g)
(wherein R
1
and R
2
individually represent a hydrogen atom or hydrocarbon group having 1-20 carbon atoms, R
3
is an alkyl group, alkenyl group, aryl group, or cycloalkyl group, each having 10 or less carbon atoms, R
4
is a hydrogen atom, halogen atom, or hydrocarbon group having 1-20 carbon atoms, f and h are an integer of 0-5, and g is an integer of 1-3), provided that at least one of A
1
to A
4
is an alkoxysilyl group or aryloxysilyl group, Y represents —CH
2
— or —O—, and m is 0 or 1, and a recurring unit (b) shown by the following formula (2),
wherein B
1
, B
2
, B
3
, and B
4
individually represent a hydrogen atom or an alkyl group, aryl group, alkenyl group, or cycloalkyl group each havi
Hashiguchi Yuuichi
Kanamori Tarou
Kawahara Kouji
Maruyama Yooichiroh
Ohkita Kenzo
JSR Corporation
Wilson D. R.
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