 |
Claims  |
|
|
What is claimed is:
1. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from an olefin thermoplastic elastomer (2) which
comprises a crystalline polyolefin resin (A) and a crosslinked olefin
rubber (C); and
(II) a skin layer formed from an olefin thermoplastic elastomer (3) which
comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 85 parts by
weight, and
a block copolymer or a hydrogenated block copolymer (B) in an amount of 15
to 80 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units contained in the isoprene polymer block or the isoprene/butadiene
copolymer block,
the total amount of said components (A) and (B) which form the skin layer
(II) being 100 parts by weight.
2. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from an olefin thermoplastic elastomer (2) which
comprises a crystalline polyolefin resin (A) and a crosslinked olefin
rubber (C); and
(II) a skin layer formed from an olefin thermoplastic elastomer (4) which
comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 85 parts by
weight,
a block copolymer or a hydrogenated block copolymer (B) in an amount of 12
to 79 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units contained in the isoprene polymer block or the isoprene/butadiene
copolymer block, and
a block copolymer or a hydrogenated block copolymer (D) in an amount of 1
to 30 parts by weight, said block copolymers each comprising:
(c) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(d) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains not more than 30% of
isoprene units bonding at 1,2- or 3,4-positions relative to the total
isoprene units contained in the isoprene polymer block or the
isoprene/butadiene copolymer block, or (e) a butadiene polymer block,
the total amount of said components (A), (B) and (D) which all form the
skin layer (II) being 100 parts by weight.
3. The thermoplastic elastomer laminate as claimed in claim 2, wherein the
olefin thermoplastic elastomer (4) further comprises an olefin rubber (C)
in an amount of 1 to 30 parts by weight and/or a softening agent (E) in an
amount of 1 to 30 parts by weight relative to 100 parts by weight of the
total amount of said components (A), (B), (C) and (D).
4. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from an olefin thermoplastic elastomer (2) which
comprises a crystalline polyolefin resin (A) and a crosslinked olefin
rubber (C); and
(II) a skin layer formed from an olefin thermoplastic elastomer (5)
comprising partially crosslinked thermoplastic elastomer which comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 80 parts by
weight,
a block copolymer or a hydrogenated block copolymer (B) in an amount of 15
to 75 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains not more than 40% of
isoprene units bonding at 1,2- or 3,4-positions relative to the total
isoprene units contained in the isoprene polymer block or the
isoprene/butadiene copolymer block, and
an olefin rubber (C) in an amount of 5 to 65 parts by weight,
the total amount of said components (A), (B) and (C) which all form the
skin layer (II) being 100 parts by weight.
5. A thermoplastic elastomer laminate as claimed in claim 4, wherein the
thermoplastic elastomer (5) further comprises a crystalline polyolefin
resin in an amount of 5 to 50 parts by weight relative to 100 parts by
weight of the total amount of the components (A), (B) and (C).
6. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from an olefin thermoplastic elastomer (2) which
comprises a crystalline polyolefin resin (A) and a crosslinked olefin
rubber (C); and
(II) a skin layer formed from an olefin thermoplastic elastomer (6) which
comprises:
a thermoplastic elastomer (1) in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and a crosslinked
olefin rubber (C), and
a block copolymer or a hydrogenated block copolymer (B) in an amount of 20
to 90 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains not more than 40% of
isoprene units bonding at 1,2- or 3,4-positions relative to the total
isoprene units contained in the isoprene polymer block or the
isoprene/butadiene copolymer block,
the total amount of said components (1) and (B) which form the skin layer
(II) being 100 parts by weight.
7. A thermoplastic elastomer laminate as claimed in claim 6, wherein the
thermoplastic elastomer (6) further comprises at least one element
selected from the group consisting of a crystalline polyolefin resin (A)
in an amount of 5 to 100 parts by weight, an olefin rubber (C) in an
amount of 5 to 100 parts by weight and a softening agent (E) in an amount
of 3 to 100 parts by weight relative to 100 parts by weight of the total
amount of the components (1) and (B).
8. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from a crystalline polyolefin resin; and
(II) a skin layer formed from an olefin thermoplastic elastomer (3) which
comprises:
a crystalline polyolefin resin in an amount of 20 to 85 parts by weight,
and
a block copolymer or a hydrogenated block copolymer (B) in an amount of 15
to 80 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains not more than 40% of
isoprene units bonding at 1,2- or 3,4-positions relative to the total
isoprene units contained in the isoprene polymer block or the
isoprene/butadiene copolymer block,
the total amount of said crystalline polyolefin resin and said component
(B) which form the skin layer (II) being 100 parts by weight.
9. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from a crystalline polyolefin resin; and
(II) a skin layer formed from an olefin thermoplastic elastomer (4) which
comprises:
a crystalline polyolefin resin an amount of 20 to 85 parts by weight,
a block copolymer or a hydrogenated block copolymer (B) in an amount of 12
to 79 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units contained in the isoprene polymer block or the isoprene/butadiene
copolymer block, and
a block copolymer or a hydrogenated block copolymer (D) in an amount of 1
to 30 parts by weight, said block copolymers each comprising:
(c) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(d) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains not more than 30% of
isoprene units bonding at 1,2- or 3,4-positions relative to the total
isoprene units contained in the isoprene polymer block or the
isoprene/butadiene copolymer block, or (e) a butadiene polymer block,
the total amount of said crystalline polyolefin resin, said component (B)
and said component (D) which form the skin layer (II) being 100 parts by
weight.
10. The thermoplastic elastomer laminate as claimed in claim 9, wherein the
thermoplastic elastomer (4) further comprises an olefin rubber (C) in an
amount of 1 to 40 parts by weight and/or a softening agent weight and/or a
softening agent (E) in an amount of 1 to 40 parts by weight based on 100
parts by weight of the total amount of the crystalline polyolefin resin,
the block copolymer (B) and the block copolymer (D) which form the skin
layer (II).
11. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from a crystalline polyolefin resin; and
(II) a skin layer formed from an olefin thermoplastic elastomer (5)
comprising partially crosslinked thermoplastic elastomer which comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 80 parts by
weight,
a block copolymer or a hydrogenated block copolymer (B) in an amount of 15
to 75 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units contained in the isoprene polymer block or the isoprene/butadiene
copolymer block, and
an olefin rubber (C) in an amount of 5 to 65 parts by weight,
the total amount of said components (A), (B) and (C) which form the skin
layer (II) being 100 parts by weight.
12. A thermoplastic elastomer laminate as claimed in claim 11, wherein the
thermoplastic elastomer (5) further comprises a crystalline polyolefin
resin an amount of 5 to 50 parts by weight relative to 100 parts by weight
of the total amount of the components (A), (B) and (C).
13. A thermoplastic elastomer laminate comprising:
(I) a substrate formed from a crystalline polyolefin resin; and
(II) a skin layer formed from an olefin thermoplastic elastomer (6) which
comprises:
a thermoplastic elastomer (1) in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and a crosslinked
olefin rubber (C), and
a block copolymer or a hydrogenated block copolymer (B) in an amount of 20
to 90 parts by weight, said block copolymers each comprising:
(a) a polymer block of a styrene selected from the group consisting of
styrene, .alpha.-methylstyrene, 3-methylstyrene, 4-propylstyrene,
4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene and
4-(phenylbutyl)styrene, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units contained in the isoprene polymer block or the isoprene/butadiene
copolymer block,
the total amount of said components (1) and (B) which form the skin layer
(II) being 100 parts by weight.
14. A thermoplastic elastomer laminate as claimed in claim 13, wherein the
thermoplastic elastomer (6) further comprises at least one element
selected from the group consisting of a crystalline polyolefin resin (A)
in an amount of 5 to 100 parts by weight, an olefin rubber (C) in an
amount of 5 to 100 parts by weight and a softening agent (E) in an amount
of 3 to 100 parts by weight relative to 100 parts by weight of the total
amount of the components (1) and (B). |
|
 |
|
 |
Claims |
|
|
|
Description |
|
|
FIELD OF THE INVENTION
The present invention relates to olefin thermoplastic elastomers and
laminates thereof. More particularly, the invention relates to olefin
thermoplastic elastomers which can be molded into articles of high scratch
resistance and relates to olefin thermoplastic elastomer laminates of high
scratch resistance which can be favorably used for automobile exterior
trim parts, etc.
BACKGROUND OF THE INVENTION
Vinyl chloride resins have been conventionally widely used for side
protection moles of automobiles. The vinyl chloride resins are very
suitable for such uses because they are excellent in scratch resistance
and available at a low price. However, the vinyl chloride resins generate
harmful gas when burned, and hence there is involved a problem of
environmental pollution.
By the way, olefin thermoplastic elastomers are used widely for automobile
parts, industrial machine parts, electric and electronic parts, building
materials, etc, as elastomers suitable for saving energy or saving natural
resource type, particularly as replacements for vulcanized rubbers,
because they are lightweight and can be easily recycled.
Further, from the viewpoint of the protection of earth environment, the
vinyl chloride resins which generate harmful gas when burned have been
recently replaced with the olefin thermoplastic elastomers which generate
no harmful gas.
However, the molded articles produced from the conventional olefin
thermoplastic elastomers are inferior in scratch resistance to the molded
articles produced from the vinyl chloride resins, and therefore, an
improvement of the scratch resistance has been eagerly desired for the
olefin thermoplastic elastomers.
Under such circumstances as mentioned above, the present inventors have
earnestly studied on the olefin thermoplastic elastomers having high
scratch resistance and molded articles thereof. As a result, they have
found the followings and accomplished the present invention.
(1) when a crystalline polyolefin resin, a specific block copolymer and an
olefin rubber are blended in a specific ratio, there can be obtained an
olefin thermoplastic elastomer capable of providing a molded article of
high scratch resistance.
(2) When a partially or perfectly crosslinked thermoplastic elastomer which
comprises a crystalline polyolefin resin and an olefin rubber, and a
specific block copolymer are blended in a specific ratio, there can be
obtained an olefin thermoplastic elastomer capable of providing a molded
article of high scratch resistance.
(3) When a crystalline polyolefin resin (or a thermoplastic elastomer), a
specific block copolymer, and any one of silicone oil, an ester of
aliphatic alcohol and a dicarboxylic acid or a fatty acid and a fluorine
polymer are blended in a specific ratio, there can be obtained an olefin
thermoplastic elastomer capable of providing a molded article of high
scratch resistance.
(4) when a laminate comprising a substrate which is formed from a partially
or perfectly crosslinked thermoplastic elastomer comprising a crystalline
polyolefin resin and an olefin rubber and a skin layer which is formed
from a thermoplastic elastomer comprising a crystalline polyolefin resin
and a specific block copolymer in a specific ratio is prepared, there can
be obtained a thermoplastic elastomer laminate of High scratch resistance
and high heat resistance which is lightweight, can be easily recycled and
generate no harmful gas when burned.
(5) When a laminate comprising a substrate which is formed from a
crystalline polyolefin resin and a skin layer which is formed from a
thermoplastic elastomer comprising a crystalline polyolefin resin and a
specific block copolymer in a specific ratio is prepared, there can be
obtained a thermoplastic elastomer laminate of high scratch resistance and
high heat resistance which is lightweight, can be easily recycled and
generate no harmful gas when burned.
OBJECT OF THE INVENTION
The present invention is intended to solve such problems associated with
the prior art technique as mentioned above, and it is an object of the
invention to provide olefin thermoplastic elastomers capable of providing
molded articles of high scratch resistance which are lightweight, can be
easily recycled, and generate no harmful gas even when subjected to
thermal disposal.
It is another object of the invention to provide thermoplastic elastomer
laminates of high scratch resistance and high heat resistance which are
lightweight, can be easily recycled, and generate no harmful gas even when
subjected to thermal disposal.
SUMMARY OF THE INVENTION
The first olefin thermoplastic elastomer according to the invention
comprises a partially crosslinked thermoplastic elastomer which comprises:
›I! a crystalline polyolefin resin (A) in an amount of 20 to 80 parts by
weight;
›II! a block copolymer (B) in an amount of 15 to 75 parts by weight, which
may be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units; and
›III! an olefin rubber (C) in an amount of 5 to 65 parts by weight;
the total amount of said components (A), (B) and (C) being 100 parts by
weight.
The second olefin thermoplastic elastomer according to the invention
comprises an olefin thermoplastic elastomer which is partially crosslinked
and comprises:
›I! a crystalline polyolefin resin (A) in an amount of 20 to 85 parts by
weight;
›II! a block copolymer (B) in an amount of 15 to 80 parts by weight, which
may be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said components (A) and (B) being 100 parts by weight;
and
›III! at least one element selected from the group consisting of (a)
silicone oil, (b) an ester of aliphatic alcohol and a dicarboxylic acid or
a fatty acid and (c) a fluorine polymer in an amount of 0.01 to 10 parts
by weight.
The third olefin thermoplastic elastomer according to the invention
comprises an olefin thermoplastic elastomer comprising:
›I! a thermoplastic elastomer ›1! in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and an olefin rubber
(C) and is partially or perfectly crosslinked; and
›II! a block copolymer (B) in an amount of 20 to 90 parts by weight, which
may be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units;
the total amount of said components ›1! and (B) being 100 parts by weight,
The fourth olefin thermoplastic elastomer according to the invention
comprises an olefin thermoplastic elastomer comprising:
›I! a thermoplastic elastomer ›1! in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and an olefin rubber
(C) and is partially or perfectly crosslinked;
›II! a block copolymer (B) in an amount of 20 to 90 parts by weight, which
may be hydrogenated and comprises:
(a) polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said components ›1! and (B) being 100 parts by weight;
and
›III! at least one element selected from the group consisting of (a)
silicone oil, (b) an ester of aliphatic alcohol and a dicarboxylic acid or
a fatty acid and (c) a fluorine polymer in an amount of 0.01 to 10 parts
by weight.
The first thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a thermoplastic elastomer ›2! which comprises a
crystalline polyolefin resin (A) and an olefin rubber (C) and is partially
or perfectly crosslinked; and
›II! a skin layer formed from a thermoplastic elastomer ›3! which
comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 85 parts by
weight, and
a block copolymer (B) in an amount of 15 to 80 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said components (A) and (B) being 100 parts by weight.
The second thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a thermoplastic elastomer ›2! which comprises a
crystalline polyolefin resin (A) and an olefin rubber (C) and is partially
or perfectly crosslinked; and
›II! a skin layer formed from a thermoplastic elastomer which is partially
crosslinked and comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 80 parts by
weight,
a block copolymer (J) in an amount of 15 to 75 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units, and
an olefin rubber (C) in an amount of 5 to 65 parts by weight,
the total amount of said components (A), (B) and (C) being 100 parts by
weight.
The third thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a thermoplastic elastomer ›2! which comprises a
crystalline polyolefin resin (A) and an olefin rubber (C) and is partially
or perfectly crosslinked; and
›II! a skin layer formed from a thermoplastic elastomer which comprises:
a thermoplastic elastomer ›1! in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and an olefin rubber
(C) and is partially or perfectly crosslinked, and
a block copolymer (B) in an amount of 20 to 90 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said components ›1! and (B) being 100 parts by weight.
The fourth thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a crystalline polyolefin resin; and
›II! a skin layer formed from a thermoplastic elastomer which comprises:
a crystalline polyolefin resin in an amount of 20 to 85 parts by weight,
and
a block copolymer (B) in an amount of 15 to 80 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said crystalline polyolefin resin and said component
(B) being 100 parts by weight.
The fifth thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a crystalline polyolefin resin; and
›II! a skin layer formed from a thermoplastic elastomer which is partially
crosslinked and comprises:
a crystalline polyolefin resin (A) in an amount of 20 to 80 parts by
weight,
a block copolymer (B) in an amount of 15 to 75 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units, and
an olefin rubber (C) in an amount of 5 to 65 parts by weight,
the total amount of said components (A), (B) and (C) being 100 parts by
weight.
The sixth thermoplastic elastomer laminate according to the invention is a
thermoplastic elastomer laminate comprising:
›I! a substrate formed from a crystalline polyolefin resin; and
›II! a skin layer formed from a thermoplastic elastomer which comprises:
a thermoplastic elastomer ›1! in an amount of 10 to 80 parts by weight,
which comprises a crystalline polyolefin resin (A) and an olefin rubber
(C) and is partially or perfectly crosslinked, and
a block copolymer (B) in an amount of 20 to 90 parts by weight, which may
be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) a polymer or copolymer block which is an isoprene polymer block or an
isoprene/butadiene copolymer block and contains at least 40% of isoprene
units bonding at 1,2- or 3,4-positions relative to the total isoprene
units,
the total amount of said components ›1! and (B) being 100 parts by weight.
DETAILED DESCRIPTION OF THE INVENTION
The olefin thermoplastic elastomers and the laminates thereof according to
the invention will be described in detail hereinafter.
The first olefin thermoplastic elastomer of the invention is now described.
The first olefin thermoplastic elastomer according to the invention
comprises a partially crosslinked thermoplastic elastomer which comprises:
›I! a crystalline polyolefin resin (A);
›II! a block copolymer (B) which may be hydrogenated and comprises:
(a) a polymer block of styrene or its derivative, and
(b) an isoprene polymer block or a specific isoprene/butadiene copolymer
block; and
›III! an olefin rubber (C).
The first olefin thermoplastic elastomer of the invention may further
comprise a crystalline polyolefin resin other than the partially
crosslinked thermoplastic elastomer.
Crystalline polyolefin resin (A)
The crystalline polyolefin resin (A) for the use in the invention is, for
example, a homopolymer or a copolymer of an .alpha.-olefin having 2 to 20
carbon atoms.
Examples of the crystalline polyolefin resin (A) include homopolymers and
copolymers described below.
(1) Ethylene homopolymer
The ethylene homopolymer may be prepared by any one of a low-pressure
process and a high-pressure process.
(2) Copolymers of ethylene and not more than 10% by mol of .alpha.-olefins
other than ethylene or vinyl monomers such as vinyl acetate and ethyl
acrylate
(3) Propylene homopolymer
(4) Random copolymers of propylene and not more than 10% by mol of
.alpha.-olefins other than propylene
(5) Block copolymers of propylene and not more than 30% by mol of
.alpha.-olefins other than propylene
(6) 1-Butene homopolymer
(7) Random copolymers of 1-butene and not more than 10% by mol of
.alpha.-olefins other than 1-butene
(8) 4-Methyl-1-pentene homopolymer
(9) Random copolymers of 4-methyl-1-pentene and not more than 20% by mol of
.alpha.-olefins other than 4-methyl-1-pentene
Examples of the .alpha.-olefins include ethylene, propylene, 1-butene,
4-methyl-1-pentene, 1-hexene and 1-octene.
Of the above crystalline polyolefin resins, particularly preferred are a
propylene homopolymer and a propylene/.alpha.-olefin copolymer having a
propylene content of not less than 50% by mol.
The crystalline polyolefin resins described above can be used singly or in
combination.
The crystalline polyolefin resin (A) has a melt flow rate (MFR, measured in
accordance with ASTM D 1238 at 230.degree. C. under a load of 2.16 kg,) of
preferably 0.01 to 100 g/10 min, more preferably 0.3 to 70 g/10 min.
The crystallinity of the crystalline polyolefin resin (A), as measured by
X-ray diffractometry, is in the range of usually 5 to 100%, preferably 20
to 80%.
In the first olefin thermoplastic elastomer of the invention, the
crystalline polyolefin resin (A) is used in an amount of 20 to 80 parts by
weight, preferably 30 to 70 parts by weight, more preferably 35 to 65
parts by weight, based on 100 parts by weight of the total amount of the
crystalline polyolefin resin (A), the block copolymer (B) and the olefin
rubber (C).
If the crystalline polyolefin resin (A) is used in such an amount as
defined above, a thermoplastic elastomer having good moldability and
capable of providing a molded article excellent in scratch resistance and
heat resistance can be obtained.
Block copolymer (B)
The block copolymer (B) for the use in the invention comprises (a) a
polymer block of styrene or its derivative and (b) an isoprene polymer
block or an isoprene/butadiene copolymer block, and may be hydrogenated.
The polymer component constituting the block (a) is styrene or its
derivative.
Examples of styrene and its derivatives include .alpha.-methylstyrene,
3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene,
2-ethyl-4-benzylstyrene and 4-(phenylbutyl)styrene. The polymer component
constituting the block (a) is preferably styrene or .alpha.-methylstyrene.
The polymer or the copolymer constituting the block (b) is an isoprene
polymer or an isoprene/butadiene copolymer, and the following isoprene
units bonding to their adjacent bonding units at 1,2-positions
(Hereinafter referred to as "1,2-bonds") and 3,4-positions (Hereinafter
referred to as "3,4-bonds") in the isoprene polymer portion are contained
in an amount of not less than 40%, preferably not less than 45%.
##STR1##
The content of the "1,2-bonds" and the "3,4-bonds" in the isoprene portion
can be measured by the method disclosed in Japanese Patent Laid-Open
Publication No. 1990.
When the content of the "1,2-bonds" and the "3,4-bonds" in the isoprene
polymer portion is not less than 40%, a thermoplastic elastomer capable of
providing a molded article excellent in scratch resistance can be
obtained.
In the block copolymer (B), the polymer block of styrene or its derivative
(a) is contained in an amount of preferably 5 to 50% by weight, more
preferably 10 to 45% by weight; and the isoprene polymer block or
isoprene/butadiene copolymer block (b) is contained in an amount of
preferably 95 to 50% by weight, more preferably 90 to 55% by weight.
In the present invention, the block copolymer (B) is preferably
hydrogenated. If the hydrogenated block copolymer is used as the block
copolymer, a thermoplastic elastomer capable of providing a molded article
excellent in scratch resistance and heat resistance can be obtained.
The block copolymer (B) used in the invention has a melt flow rate (MFR,
measured in accordance with ASTM D 1238 at 230.degree. C. under a load of
2,16 kg,) of preferably 0.01 to 30 g/10 min, more preferably 0.01 to 10
g/10 min. If the block copolymer (B) having such a melt flow rate as
defined above is used, a thermoplastic elastomer capable of providing a
molded article excellent in scratch resistance can be obtained.
As the block form of the block copolymer (B) used for the invention, a form
of block (a)--block (b)--block (a) is most preferred, but the block form
is in no way limited thereto.
The block copolymer (B) can be prepared by, for example, the following
processes disclosed in Japanese Patent Laid-Open Publication No.
300250/1990.
(1) A process of successively polymerizing styrene or its derivative and an
isoprene or an isoprene/butadiene mixture using an alkyllithium compound
as an initiator.
(2) A process of polymerizing styrene or its derivative, then polymerizing
an isoprene or an isoprene/butadiene mixture and coupling them with a
coupling agent.
(3) A process of successively polymerizing an isoprene or an
isoprene/butadiene mixture and styrene or its derivative using a dilithium
compound as an initiator.
Details of the process for preparing the block copolymer (B) are described
in, for example, Japanese Patent Laid-Open Publications No. 300250/1990
and No. 45646/1991.
When the block copolymer (B) prepared as above is subjected to
hydrogenation, a hydrogenated block copolymer (B) can be obtained. The
block to be hydrogenated is the isoprene polymer block or
isoprene/butadiene copolymer block (b).
In the first olefin thermoplastic elastomer of the invention, the block
copolymer (B) is used in an amount of 15 to 75 parts by weight, preferably
20 to 60 parts by weight, more preferably 25 to 55 parts by weight, based
on 100 parts by weight of the total amount of the crystalline polyolefin
resin (A), the block copolymer (B) and the olefin rubber (C).
If the block copolymer (B) is used in such an amount as defined above, a
thermoplastic elastomer capable of providing a molded article excellent in
scratch resistance and heat resistance can be obtained.
Olefin rubber (C)
The olefin rubber (C) for the use in the invention is an amorphous random
elastomeric copolymer containing an .alpha.-olefin of 2 to 20 carbon atoms
in an amount of not less than 50% by mol, and includes an amorphous
.alpha.-olefin copolymer comprising two or more kinds of .alpha.-olefins
and an .alpha.-olefin/non-conjugated diene copolymer comprising two or
more kinds of .alpha.-olefins and non-conjugated diene.
Concrete examples of the olefin rubber (C) includes the following rubbers.
(1) Ethylene/.alpha.-olefin copolymer rubber ›ethylene/.alpha.-olefin
(molar ratio)=about 90/10 to 50/50)!
(2) Ethylene/.alpha.-olefin/non-conjugated diene copolymer rubber
›ethylene/.alpha.-olefin (molar ratio)=about 90/10 to 50/50)!
(3) Propylene/.alpha.-olefin copolymer rubber ›propylene/.alpha.-olefin
(molar ratio)=about 90/10 to 50/50)!
(4) Butene/.alpha.-olefin copolymer rubber ›butene/.alpha.-olefin (molar
ratio)=about 90/10 to 50/50)!
Examples of the .alpha.-olefins are the same as those constituting the
above-mentioned crystalline polyolefin resin (A).
Examples of the non-conjugated dienes include dicyclopentadiene,
1,4-hexadiene, cyclooctadiene, methylene norbornene and ethylidene
norbornene.
The ethylene/.alpha.-olefin/non-conjugated diene copolymer rubber (2) in
which such non-conjugated diene as mentioned above is copolymerized has an
iodine value of preferably not more than 25.
Each of the copolymer rubbers (1) to (4) has a Mooney viscosity ›ML.sub.1+4
(100.degree. C.)! of 10 to 250, preferably 30 to 150.
In the first olefin thermoplastic elastomer of the invention, the olefin
rubber (C) is used in an amount of 5 to 65 parts by weight, preferably 10
to 50 parts by weight, more preferably 10 to 40 parts by weight, based on
100 parts by weight of the total amount of the crystalline polyolefin
resin (A), the block copolymer (B) and the olefin rubber (C).
If the olefin rubber (C) is used in such an amount as defined above, a
thermoplastic elastomer capable of providing a molded article excellent in
scratch resistance and flexibility can be obtained.
Other rubbers than the olefin rubber (C) may be used in combination with
the olefin rubber (C), with the proviso that the objects of the invention
are not marred.
Examples of other rubbers than the olefin rubber (C) include diene rubbers
such as styrene/butadiene rubber (SBR), nitrile rubber (NBR), natural
rubber (NR) and butyl rubber (IIR), and polyisobutylene rubber.
Block copolymer (D)
The first olefin thermoplastic elastomer of the invention which is
partially crosslinked may further contain, as its component, a block
copolymer (D) which may be hydrogenated and comprises a polymer block of
styrene or its derivative (c), and an isoprene polymer block or an
isoprene/butadiene copolymer block (d) or a butadiene polymer block (e),
if necessary, in addition to the crystalline polyolefin resin (A), the
block copolymer (B) and the olefin rubber (C).
The polymer component constituting the block copolymer (D) is styrene or
its derivative.
Examples of the styrene and its derivatives are the same as those described
above for the block copolymer (B). The polymer component for constituting
the block copolymer (D) is preferably styrene or .alpha.-methylstyrene.
The polymer or the copolymer constituting the block (d) is an isoprene
polymer or an isoprene/butadiene copolymer, and the "1,2-bonds" and the
"3,4-bonds" in the isoprene polymer portion are contained in an amount of
not more than 30%, preferably not more than 25%.
When the content of the "1,2-bonds" and the "3,4-bonds" in the isoprene
polymer portion is not more than 30%, a thermoplastic elastomer capable of
providing a molded article having good appearance can be obtained.
The block copolymer (D) used in the invention may be formed from the block
(c) and the block (d), or may be formed from the block (c) and the
butadiene polymer block (e).
In the block copolymer (D), the polymer block of styrene or its derivative
(c) is contained in an amount of preferably 5 to 50% by weight, more
preferably 10 to 45% by weight; and the isoprene polymer block or
isoprene/butadiene copolymer block (d) or the butadiene polymer block (e)
is contained in an amount of preferably 95 to 50% by weight, more
preferably 90 to 55% by weight.
In the present invention, the block copolymer (D) is preferably
hydrogenated. If the hydrogenated block copolymer is used as the block
copolymer (D), a thermoplastic elastomer capable of providing a molded
article excellent in scratch resistance and heat resistance can be
obtained.
The block copolymer (D) used in the present invention has a melt flow rate
(MFR, measured in accordance with ASTM D 1238 at 230.degree. C. under a
load of 2.16 kg,) of preferably 0.01 to 100 g/10 min, more preferably 0.01
to 50 g/10 min. If the block copolymer (D) having such a melt flow rate as
defined above is used, a thermoplastic elastomer capable of providing a
molded article excellent in scratch resistance can be obtained.
As the block form of the block copolymer (D) used for the invention, a form
of block (c)--block (d) or (e)--block (c) is most preferred, but the block
form is in no way limited thereto.
The block copolymer (D) which may be hydrogenated can be prepared, for
example, in the same manner as described above to prepare the block
copolymer (B).
In the preparation of the hydrogenated block copolymer, the block to be
hydrogenated is the isoprene polymer block or isoprene/butadiene copolymer
block (d) or the butadiene polymer block (e).
< | | |
