Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-05-12
2002-10-01
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...
C526S132000, C526S133000, C526S134000, C526S159000, C526S160000, C526S348200, C526S348500, C526S348600, C526S280000
Reexamination Certificate
active
06458901
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a propylene copolymer and a thermoplastic resin composition. In particular, the present invention relates to a novel propylene copolymer, which is mixed with a thermoplastic resin such as polypropylene to provide a thermoplastic resin composition having excellent flexibility, transparency, resistance to whitening on bending, scratch resistance and heat resistance, and to a thermoplastic resin composition comprising such a propylene copolymer and a thermoplastic resin.
BACKGROUND ART
Ethylene-propylene-non-conjugated diene copolymers (EPDM) have good ozone resistance, weather resistance, heat-aging resistance, chemical resistance, etc., since they have no double bond in their backbones, and thus they are widely used in crosslinking rubber applications or resin modifier applications. In particular, in the resin modifier applications, it is known to produce a thermoplastic resin having good tensile properties, compression set and impact resistance by finely dispersing EPDM in a resin matrix by a dynamic crosslinking method comprising blending EPDM in the resin matrix, and kneading them with a crosslinking agent to crosslink EPDM. Recently, the demand for the use of polyolefin materials increases also in the fields where soft vinyl chloride resins have been used. In such fields, the higher performances are required with regard to flexibility, heat resistance, scratch resistance and transparency. However, the polyolefin materials comprising EPDM may not always reach the required levels of such properties.
To deal with the environmental pollution issues, the demand for substitute materials for soft vinyl chloride resins increases in the applications where the soft vinyl chloride resins have been used. With such a background, there are proposed a thermoplastic resin composition having good flexibility, transparency, mechanical strength, resistance to whitening, cold resistance, etc., which is prepared by blending a specific hydrogenated conjugated diene-styrene copolymer with a thermoplastic resin such as polypropylene (JP-A-6-57087, JP-A-6-271717, etc.), and a thermoplastic resin composition having good flexibility, transparency, mechanical strength, resistance to whitening and cold resistance, which contains a crystalline polypropylene resin and an ethylene-a-olefin copolymer as a soften material consisting of olefinic components (JP-A-7-102126, etc.)
The latter composition may be a material having the properties relatively close to the required levels as a substitute material for the soft vinyl chloride resins among olefinic materials containing neither chlorine nor aromatic vinyl compounds. However, this composition has a problem, that is, the surface tackiness due to the ethylene-&agr;-olefin copolymer, as described in JP-A-8-301927, and has not been practically used.
To improve such tackiness, JP-A-8-301927 and JP-A-9-104720 proposed a method for crosslinking an ethylene-&agr;-olefin copolymer with electron beams or peroxide compounds. However, such a method is not still satisfactory.
Under such circumstances, the present inventors have proposed a propylene copolymer comprising propylene-&agr;-olefin, or propylene-&agr;-olefin-ethylene as a novel material which is advantageously used in the production of olefinic soft materials (Japanese Patent Application Nos. 9-312036 and 10-190256). However, molded products of a resin composition comprising such a propylene copolymer have surface tackiness in the practical property test, in particular, the high-temperature accelerated weathering test. Thus, such a resin composition does not have sufficient properties for the use in applications requiring heat resistance, for example, automobile interior applications which may encounter high-temperature environments.
SUMMARY OF THE INVENTION
In view of such prior arts, the present inventors have made extensive study on propylene copolymers, and found that a material comprising a novel propylene copolymer as a modifier has better flexibility, transparency, resistance to whitening on bending and scratch resistance than the conventional thermoplastic resin compositions comprising EPDM as a modifier, and that the tackiness, which is the problem under the specific application conditions in the prior art, can be improved by the use of a novel propylene copolymer.
One object of the present invention is to provide a novel propylene copolymer which is mixed with a thermoplastic resin such as polypropylene to provide a thermoplastic resin composition having excellent flexibility, transparency, resistance to whitening on bending, scratch resistance and heat resistance.
Another object of the present invention is to provide a novel propylene copolymer, which can improve the tackiness that is the problem under the specific application conditions in the prior art, when it is used as a modifier of a thermoplastic resin.
According to the first aspect of the present invention, there is provided a propylene copolymer comprising propylene, at least one olefin selected from the group consisting of olefins having 2 to 20 carbon atoms except propylene, and a cyclic olefin, wherein the total number of carbon atoms of the monomers except the cyclic olefin is at least 7 (hereinafter referred to as the first invention).
According to the second aspect of the present invention, there is provide an additive for a thermoplastic resin composition, comprising the propylene copolymer of the first invention.
According to the third aspect of the present invention, there is provided a thermoplastic resin composition comprising the propylene copolymer of the firs invention and a thermoplastic resin.
DETAILED DESCRIPTION OF THE INVENTION
The propylene copolymer of the present invention comprises propylene, at least one olefin selected from the group consisting of olefins having 2 to 20 carbon atoms except propylene, and a cyclic olefin, and is characterized in that the total number of carbon atoms of the monomers except the cyclic olefin is at least 7.
Examples of the olefins having 2 to 20 carbon atoms except propylene include an olefin of the formula [IV]:
wherein R
1
is a hydrogen atom or a linear or branched alkyl group having 2 to 18 carbon atoms.
Specific examples of such olefins include ethylene; linear olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, etc.; and branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, -1-4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1-pentene, etc.
Examples of the combinations of olefins in which the total number of the carbon atoms of the monomers except the cyclic olefin is at least 7 include propylene/1-butene, propylene/1-hexene, propylene/1-octene, propylene/1-butene/1-hexene, propylene/1-butene/1-octene, propylene/1-butene/1-hexene/1-octene, propylene/1-butene/ethylene, propylene/1-hexene/ethylene, propylene/1-octene/ethylene, propylene/1-butene/1-hexene/ethylene, propylene/1-butene/1-octene/ethylene, propylene/1-butene/1-hexene/1-octene/ethylene, and the like.
The cyclic olefin to be used in the propylene copolymer of the present invention is a cyclic compound having at least one ring with at least 4 carbon atoms, and at least one double bond in the molecules which may optionally be substituted with various substituents. A specific example of such a cyclic olefin is a compound of the formula [V] or [VI]:
wherein n, m and 1 are each an integer of 0 or larger; C
1
to C
15
are carbon atoms, and C
1
and C
2
forms a polymerizable double bond; R
1
to R
12
and R
14
to R
17
represent independently each other a hydrogen atom, a halogen atom, a hydroxyl group, an amino group or an organic group having 1 to 20 carbon atoms; C
3
and C
6
, and C
8
and C
11
in the formula [V] may be bonded through (C
7
)
n
and (C
12
)
n
, respectively;
R
9
and R
10
and R
11
and R
12
may form a ring through a residu
Hozumi Hidetake
Johoji Hirofumi
Yamamoto Keisaku
Cheung William K
Sumitomo Chemical Company Limited
Wu David W.
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