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
1999-05-21
2001-08-21
Gorr, Rachel (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S071000, C525S063000, C525S077000, C525S080000, C525S084000, C525S085000, C525S086000, C525S087000, C525S170000, C525S183000, C525S227000, C525S228000, C525S238000, C525S241000
Reexamination Certificate
active
06277913
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition and interior or exterior parts for vehicles using thereof, which are excellent in flexibility, surface appearance, weatherability, moldability and heat deformation property and has low tackiness at a high temperature.
In recent years, a resin such as PVC, olefin or urethane is employed as a flexible resin in the field of an automobile, electric appliances for domestic use and OA apparatus, and the like. Among those, a flexible resin of PVC is widely employed as a flexible PVC. But a PVC flexible resin has a problem in weight loss at heating and migration of a plasticizer, since much plasticizer need to be added thereto. In a flexible resin other than PVC such as a flexible resin of styrene, a resin having a segment of isoprene, butadiene or the like was proposed. But it is on demerit especially in economy from the viewpoint of equipment and productivity, and has high tackiness at a high temperature, since it is a block copolymer of a hard segment and a soft segment and it need to be prepared by the particular polymerization method in a non-aqueous solvent. On the other hand an flexible resin of olefin is difficult to be applied and printed, and has a problem of a less surface modification property.
As to a resin of styrene, Japanese Unexamined Patent Publication No. 20346/1984 discloses a method of adding a particular plasticizer to a styrene resin reinforced by a rubber. But it is not sufficient because of volatilization of the plasticizer. As to a composition of an ABS resin and a copolymer of an acrylic ester, Japanese Unexamined Patent Publication No. 179257/1983 discloses a composition comprising a styrene resin containing a rubber and a copolymer of an acrylic ester copolymer, and Japanese Unexamined Patent Publication No. 17954/1988 discloses a composition comprising a copolymer of maleimide-styrene containing a rubber, an ABS resin and a copolymer of an acrylic ester copolymer. And it is described that a molded article of the composition is excellent in a chemical resistance. However, these compositions are remarkably lack in flexibility, the resin has not been obtained, which is excellent in flexibility, surface appearance, weatherability and heat deformation property at heating, and has low tackiness at a high temperature.
And Japanese Unexamined Patent Publication No. 27336/1996 discloses a composition comprising a maleimide-styrene copolymer containing a rubber and an acrylic ester copolymer. But the resin has not been obtained, which is excellent in flexibility as the composition of the present invention.
Many graft copolymers (rubber) of ABS resin (of which matrix is a copolymer of styrene and acrylonitrile or a copolymer of styrene, acrylonitrile and maleimide) have been proposed, but there has been proposed no graft copolymers (rubber), which is suitable to a resin comprising a copolymer of maleimide-styrene-acrylonitrile and a copolymer of an acrylic ester.
An object of the present invention is to provide a thermoplastic resin composition and interior or exterior parts for vehicles molded thereof, which has no problems mentioned-above, is excellent in flexibility, surface appearance, weatherability, moldability and heat deformation property, and has low tackiness at a high temperature.
SUMMARY OF THE INVENTION
The present inventors consider that it is necessary to employ a (meth)acrylic ester copolymer (X) having the glass transition temperature not more than 20° C. in order to keep flexibility of a thermoplastic resin composition. And the present inventors also consider that it is necessary not to completely compatibilize a (meth)acrylic ester copolymer (X) and copolymer (Y) in order to give an elasticity to the thermoplastic resin composition, and to have a particular phase structure, in which a micro phase separation of matrix comprising a (meth)acrylic ester (X) and a copolymer having a high glass transition temperature or a high melting point is delicately controlled. In an occasion, it is considered to suitably employ an graft copolymer (Z) or to gently cross-link a copolymer of (meth)acrylic ester (X).
The present inventors have made intensive studies to attain the above-mentioned object and as a result, have found that a thermoplastic resin composition comprising a particular copolymer of (meth)acrylic ester (X), a copolymer (Y) having the glass transition temperature or the melting point of not less than 50° C., and an optional graft copolymer (Z) is excellent in flexibility, surface appearance, weatherability and heat deformation property, and has low tackiness at a high temperature.
Namely, the present invention relates to
a thermoplastic resin composition comprising 25 to 90 parts by weight of a (meth)acrylic ester copolymer (X), which is prepared by polymerizing 40 to 95% by weight of a (meth)acrylic ester, 0 to 40% by weight of a vinyl cyanide compound, not more than 60% by weight of an aromatic vinyl compound and 0 to 40% by weight of a monomer copolymerizable therewith, and has a glass transition temperature of not more than 20° C. and a gel content of not more than 50% by weight, 5 to 75 parts by weight of a copolymer (Y), which has a glass transition temperature or a melting point not less than 50° C., and 0 to 70 parts by weight of a graft copolymer (Z), which is prepared by polymerizing 5 to 95% by weight of a rubber polymer (A) and 5 to 95% by weight of a vinyl monomer (B), wherein the total weight of the copolymers (X), (Y) and (Z) is 100 parts by weight, and wherein hardness thereof at 20° C. measured by the method of JIS K6301 is 30 to 100 (claim
1
),
the thermoplastic resin composition of claim
1
, wherein the content of the graft copolymer (Z) is 5 to 65 parts by weight (claim
2
), the thermoplastic resin composition of claim
1
, wherein the copolymer (Y) is at least one thermoplastic resin selected from the group consisting of a styrene resin, a vinyl chloride resin, an acrylic resin, polycarbonate, an amide resin, an ester resin and an olefin resin (claim
3
),
the thermoplastic resin composition of claim
1
, wherein the copolymer (Y) is a styrene resin which is prepared by polymerizing 0 to 40% by weight of a vinyl cyanide compound, 10 to 95% by weight of an aromatic vinyl compound, 0 to 50% by weight of maleimide monomer and 0 to 40% by weight of a monomer copolymerizable therewith, wherein the total percentage being 100 (claim
4
),
the thermoplastic resin composition of claim
1
, wherein the graft copolymer (Z) is prepared by polymerizing 5 to 95 parts by weight of at least one rubber polymer (A) selected from the group consisting of a diene rubber polymer, an olefin rubber polymer, an acrylic rubber polymer and a silicone rubber polymer, which has a volume average particle size of 30 to 2,000 nm, and 5 to 95 parts by weight of a monomer mixture comprising 5 to 90% by weight of an aromatic vinyl compound, 10 to 95% by weight of at least one monomer selected from the group consisting of a (meth)acrylic ester and a vinyl cyanide compound, and 0 to 30% by weight of a monomer copolymerizable therewith, wherein the total percentage being 100 (claim
5
),
interior or exterior parts for vehicles comprising 25 to 90 parts by weight of a (meth)acrylic ester copolymer (X), which has a glass transition temperature of not more than 20° C. and a gel content of not more than 50% by weight, 5 to 75 parts by weight of a copolymer (Y) which has a glass transition temperature of not less than 50° C., and 0 to 70 parts by weight of a graft copolymer (Z), which is prepared by polymerizing 5 to 95% by weight of a rubber polymer (A) and 5 to 95% by weight of a vinyl monomer (B), and wherein surface hardness of an article molded thereof measured by the method of JIS K6301 at 20° C. is 30 to 100 (claim
6
),
the interior or exterior parts for vehicles of claim
6
, wherein the (meth)acrylic ester copolymer (X) is prepared by polymerizing 40 to 95% by weight of a (meth)acrylic ester, 0 to 60% by weight of an aromatic vinyl compound, 0 to 40% by weight o
Mishima Ikuhiro
Wada Kazuhito
Armstrong Westerman Hattori McLeland & Naughton LLP
Gorr Rachel
Kaneka Corporation
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