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E657 Abstract: Te invention rele 0 fotear made from themopasic elstomercomposton comping (one of more
Soren Hack cope (5) opdonlly- one or more ingeients belted from extender Ol filles, hardcsrepulatr, ow
improve x ack esianceinprovers, subse, UV Sublver, pgm lng agen and snoring send (0)
tne or more melalocene based poo of ene and from 8% to 4% by weigh fen spelen comonomer ang rom 3
1020 eabon atoms having debs fom 08610095 ka nda molar weight ton (ha) ess han 3
(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
(19) World Intellectual Property Organi
International Bureau
(43) International Publication Date
12 April 2001 (12.04.2001)
Ly &
(10) International Publication Number
‘WO 01/25331 Al
(1) International Patent Classification’:
23/10, A43B 1304
COL 53/02,
21) International Application Number: PCT/EPOOO9TS4
(22) International Filing Date: 4 October 2000 (04.10.2000)
(25) Filing Languag
English
(26) Publication Language: English
(80) Priority Data:
.99307867.4
{6 October 1999 (06.10.1999) EP
(71) Applicant or all designated States excep! US): SHELL
INTERNATIONALE RESEARCH MAATSCHAPPIS
[BY [NLINL}; Carel van Bylandlaan 30, NL-2596 HR
‘The Hague (NL),
Inventors; and
Inventors/Applicants for US only):
Michaet (GB/NL]; Badhuisweg 3, NL
am (NL). MAES, Caroline, Rita, N
enue Jean Monnet 1, B-1348 Otignis, Louvain-La-Newve
(BE). VERHEYDEN, Eddy [BE/BE}; Avenue Jean
Monnet 1, B-1348 Ouignies, Louvain-La-Neuve (BE).
BATT, Alan,
VOSTERS, Philippe (BE/BE]; Avenue Jean Monnet 1,
'B-1348 Otignies, Louvain-La Neuve (BE).
(81) Designated States (national: AE, AG, AL, AM, AT, AU,
AZ, BA. BB, BG, BR, BY, BZ, CA, CH, CN, CR, CU, CZ,
DE, DK, DM, DZ, FE, ES,F1. GB, GD, GE, GH, GM, HR,
HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC,LK, LR,
LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ,
NO,.NZ, PL, PT, RO, RU, SD, SE,SG, SI,SK.SL,7,TM,
‘TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW.
(84) Designated States (regional): ARIPO patent (GH, GM,
KE, LS, MW, MZ, SD, SL, SZ. TZ, UG, ZW), Eurasian
patent (AM, AZ, BY, KG, KZ, MD, RU, T3,TM), European
patent (AT. BE, CH, CY, DE, DK, FS, FT, FR, GB, GR, IE,
TT, LU, MC, NL, PT, SE), OAPI patent (BE, BJ, CF, C
CI.CM, GA, GN, GW, ML, MR, NE, SN, TD, TG).
Published:
With international search report
Before the expiration of the time limit for amending the
claims and 10 be republished in the event of receipt of
amendments
For tworletter codes and other abbreviations, refer tothe "Guid
‘ance Notes on Cades and Abbreviations” appearing at the begin:
ning of each regular issue of the PCT Gazete
(54) Title: FOOTWEAR MADE FROM A THERMOPLASTIC ELASTOMER COMPOSITION HAVING A DULL LOOK‘Wo 01/25331 ae PCT/EPOOI09764
FOOTWEAR MADE FROM A THERMOPLASTIC ELASTOMER COMPOSITION
HAVING A DULL LOOK
Field of the invention
The invention relates to footwear made from a
thermoplastic elastomer composition having a dull look.
More in particular, the invention relates to footwear,
5 such as in soles and heels.
Background of the invention
Thermoplastic elastomer compositions are based on
materials which behave like elastomeric rubbers at room
temperature, but when heated can be processed like
10 plastics. They are used in the manufacture of casual
shoes and sport shoes. The thermoplastic elastomers
(TPEs) most frequently used in the production of shoe
soles are styrenic block copolymers such as poly(styrene-
butadiene-styrene) or SBS copolymers (market share of
15 about 15%). Such compositions have advantages over
natural rubber and PVC (e.g. easy and cheap to process;
qood low temperature crack resistance and excellent grip
in wet conditions). These ‘synthetic’ soles and heels are
even replacing their leather counterparts in the upper
20 class shoe range.
Shell Chemicals published a bulletin on the
formulation of TPE compositions for footwear applications
based on an SBS copolymer sold as “KRATON” D (KRATON is a
trademark). This bulletin, TPE 4.2.2 issued December
25 1994, provides a typical formulation comprising oils
styrenic resins, ethene-vinyl acetate (EVA), polyolefins
fillers, antioxidants, UV stabilisers and other
ingredients in addition to the “KRATON” D TPE. This
bulletin also provides general information regarding the
30 compounding equipment and mixing schemes and conditions.10
15
20
30
Wo 01/25331 PCTIEPOOIO9764
-2-
A later fact sheet also available from Shell
Chemicals, KOQ02FS-99e, “Starting Formulations for
KRATON D Footwear Compounds” provides even more detailed
formulations for use in e.g., general purpose solid
soling, high hardness thin fashion soling,
hiking/mountain boots, and sneakers/slippers.
Unfortunately, mouldings based on such TPE
compositions can have a surface appearance which is less
desirable in a range of sole/footwear applications. In
particular, they lack the uniform ‘dull look’ typical of
vulcanised natural rubber. This problem may be solved by
the addition of a small amount of partially crystalline
~RBB30" sold by
JSR) to the TPE composition. However, RB830 is expensive
syndiotactic 1,2-polybutadiene (e.g
and not broadly available. It would therefore be
desirable to find an alternative TPE composition for
footwear applications having a uniform dull look
Moreover, the new composition should at least retain
important footwear properties such as Din Abrasion
Summary of the invention
The invention provides footwear made from a
thermoplastic elastomer composition comprising
(a) one or more styrenic b:
ck copolymers;
(b) -optionally- one or more ingredients selected from
extender oils, fillers, hardness regulators, flow
improvers, flex crack resistance improvers, stabilisers
UV stabilisers, pigments, blowing agents, and anti-
blocking agents; and
(c) one or more metallocene-based polyolefins of ethene
and from 8% to 40% by weight of an alpha-olefin comonomer
having from 3 to 20 carbon atoms, having a density from
0.86 to 0.95 kg/1 and a molecular weight distribution
(Mw/Mn) less than 3.
Detailed description of the invention10
15
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25
30
35
‘Wo 01/28331 PCT/EPOO/09764
3
Surprisingly, the footwear made from the TPE
compositions described above have a uniform dull look
without substantial loss of other footwear properties
The components of the TPE composition will be described
hereinafter in more detail.
Component (a)
Styrenic block copolymers are thermoplastic
elastomers having two or more distinguishable polymer
blocks, of which at least one is glassy at service
temperature but fluid at higher temperatures, and at
least one of which is elastomeric (rubbery) at service
temperature. A comprehensive review on such polymers is
provided by Messrs. Legge, H
len and Schroeder, in
“Thermoplastic Elastomers”, published by Hanser
Publishers in 1987 (ISBN 3-446-14827-2).
These block copolymers come in the form of linear
diblocks, triblocks and multiblocks (produced with
sequential polymerization techniques or difunctional
coupling agents), or branched block copolymers (using
multifunctional coupling agents and/or re-initiation
techniques).
The preferred block copolymers in accordance with the
Present invention are branched block copolymers, or a
mixture of a branched block copolymer and a linear block
copolymer. For instance, component (a) may be mixture of
a triblock or multiblock copolymer with the diblock
copolymer that has been used in the preparation of such
triblock or multiblock copolymers.
The block copolymer to be used in the compound of the
present invention may be prepared by any method known in
the art including the well known full sequential
polymerisation method, optionally in combination with
re-initiation, and the coup.
e.g. US Patents Nos. 3,231,635; 3,251,905; 3,390,207;
ng method, as illustrated in
3,598,887 and 4,219,627, in European patent application10
15
20
25
30
wo 0128331 PCT/EPOO/09764
Nos. 413,294, 387,671, 636,654 and International
application No. 94/22931
The or each glassy polymer block of the block
copolymer is made of polymerized vinylaromatic monomer
such as styrene, in an amount of at least 80 moleé on the
total monomer content of the polymer block. Styrene is
the preferred vinylaromatic monomer, but other suitable
vinylaromatic monomers include a-methylstyrene,
p-methylstyrene, m-methylstyrene, o-methylstyrene
p-tert-butylstyrene, dimethylstyrene, and various other
alkyl-substituted styrenes, alkoxy-substituted styrenes,
vinylnaphthalene and vinyl xylene. These alkyl and alkoxy
groups may contain from 1 to 6 carbon atoms, more
preferably from 1 to 4 carbon atoms. Comonomers, if
present, may be selected from (di)olefins and other
compounds copolymerizable with styrene.
Preferred styrenic block copolymers are those wherein
the or each elastomeric block of the block copolymer is
made of polymerized conjugated diene, such as butadiene
or isoprene, in an amount of at least 60 mole% on the
total monomer content of the elastomeric block. Butadiene
and isoprene are the preferred dienes, but other suitable
conjugated dienes include dienes with from 4 to 8 carbon
atoms per monomer, for example, 2-ethyl-1,3-butadiene
2,3-dimethyl-1,3-butadiene, 1,3-butadiene
1,3-pentadiene, 2,4-hexadiene, 3-ethyl-1,3-pentadiene
and mixtures thereof. These conjugated dienes may be
copolymerized in either a 1,2- or 1,4-fashion, leading to
a vinyl content in the range of 5-80. Comonomers, if
present, may be selected from vinylaromatic monomers and
other compounds copolymerizable with the diene.
Preferred block copolymers are those that are based
on styrene ("S”) and butadiene (*B’) or isoprene (“I”)
and are conventionally referred to as (SB)pX, (SI) pX, SB10
15
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25
30
35
WO 01/2531 PCT/EP00/09764
SI, SBS and SIS, wherein “X” refers to the residue of a
coupling agent, and “n” has a value of at least 2,
preferably more than 2.
These styrenic block copolymers may also be fully or
partially hydrogenated. Preferred hydrogenated styrenic
block copolymers are those wherein only the elastomeric
block is selectively hydrogenated (more than 80%
preferably more than 99% on total unsaturation). such
hydrogenated block copolymers provide improved properties
in respect of durability, sensitivity to oil and
chemicals and floor marking (i.e., leaves less markings
in indoor sports).
The content of the vinyl aromatic monomer of the
final block copolymer is preferably in the range of from
15 to 75% by weight, and more preferably 20 to 60% by
weight, based on the total block copolymer.
The total apparent molecular weight of the block
copolymer is preferably in the range from 100,000 to
500,000 g/mol, more preferably in the range from 150,000
to 400,000 g/mol. With the expression “apparent molecular
weight” as used throughout the specification is meant the
molecular weight of a polymer as measured with gel
permeation chromatography (GPC) using polystyrene
calibration standards (according to ASTM D 3536)
Suitable block copolymers include, amongst others,
those sold by Shell under the trademark “KRATON”. Other
suppliers include Enichem ("EUROPRENE’
(“CALPRENE”), Fina (“FINAPRENE”), DEXCO (“VECTOR”)
7 Repsol
Nippon Zeon (“QUINTAC”); Firestone ("STEREON’), Asahi
(“TUFPRENE”); Kuraray (“SEPTON") and others such as Chi-
Mei; Coperbo; TSRC; LCY; and Kumho (EUROPRENE, CALPRENE
FINAPRENE, VECTOR, QUINTAC, STEREON, TUFPRENE and SEPTON
are trademarks). Particularly suitable are “KRATON”
elastomeric block copolymers sold as clear grade D1101
1102, D1151, (all linear SBS/SB copolymers) D115510
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Wo 01/25331 PCTIEPO0/09764
-6-
(1inear SBS), D1184, D1186 (both branched copolymers), as
oil-extended grade D4123, D4270, D4271, KX224, D4272, and
~for high end footwear applications such as hiking and
safety boots and sports wear, hydrogenated block
copolymers G1650, G1651, G1654, G1657, and RP6917
Component (c)
Suitable metallocene polyolefins and thermoplastic
elastomer compositions containing the same are described
in European patent application No. 712,892. The
metallocene polyolefins are polyolefins produced with a
metallocene catalyst such as those described in United
States Patents Nos. 4,871,705, 5,322,728 and 5,272,236
which are hereby incorporated by reference. Such
metallocene polyolefins are available from Dow Chemical
Company under the trademark “AFFINITY” or “ENGAGE”
(ethene/octene copolymers) and from Exxon Chemical
Company under the trademark “EXACT” (ethene/butene
copolymers). The metallocene polyolefins have low
crystallinity when ethene is copolymerised with from 8%
to 408 by weight of an alpha-olefin comonomer having from
3 to 20 carbon atoms, preferably from 4 to 12 carbon
atoms. Such polyolefins have a good distribution of
ethene and the comonomer (as further explained in the
references) .
Suitably, the metallocene polyolefins have a Melt
Flow Index in the range of 0.5 to 40 g/10 min (“MFI” at
190 °C/5 kg, determined in accordance with ISO 1133).
Preferred metallocene polyolefins have an MFI in the
range of 1.0 to 30 g/10 min.
The density of suitable metallocene polyolefins
varies from 0.86 to 0.95 kg/l, preferably from 0.88 to
0.92 kg/1. Metallocene polyolefins having a density in
the range of 0.89 to 0.90 kg/l are preferred10
15
20
35
Wo 0125331 PCT/EPOO/09764
-7-
Preferred metallocene polyolefins, marketed under the
trademark “ENGAGE”, are grades 8150 (density 0.868 kg/1;
MFI 2 g/10 min); 8585 (density 0.885 kg/l; MFI 8 g/10
min); and 8440 (density 0.897 kg/l; MFI 6 g/10 min). The
latter is particularly preferred
These metallocene polyolefins may be used in amounts
in which presently crystalline syndiotactic 1,2-polybuta-
diene is used. For instance, it may be used in an amount
of from 5 to 35 phr of component (c), (phr = parts by
weight per 100 parts by weight of component (a)),
preferably in an amount of from 10 to 30 phr, most
preferably at around 20 phr.
Components (b)
Hydrocarbon extender oils are generally known as
paraffinic and/or naphthenic oils. They usually are
fractions of products deriving from petroleum refining
having less than about 30% by weight of aromatics,
measured by clay-gel analysis, and have usually a
viscosity comprised between about 100 and about 500 ssuU
at 37.8 °C (100 °C). These hydrocarbon extender oils are
commercially known, for instance with the trademark
“CATENEX SM 925” or “PROCESS KD28”, produced and sold by
Shell. The amount of extender oils used in the
composition of the present invention can range from 0 to
100, preferably from 5 to 30 phr. Higher amounts than
100 phr, however, may be used for some thermoplastic
elastomer compositions. The extender oil may be included
in the TPE, e.g., as in the oil-extended KRATON D4123
D4270, D4271, KX224, D4272 and/or VECTOR 7400D
The thermoplastic elastomer composition may comprise
other components. Such components include inorganic
fillers, such as clay, talc, silica, alumina, titanium
dioxide, carbon black, calcium carbonate, sawdust and the
like, and other pigments. The preferred fillers comprise
silica, calcium carbonate and the like and mixtures10
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Wo 01/25331 PCT/EPO0/09764
-8-
thereof. The particle sizes may vary from 1 to
50 micrometers, but are usually smaller (e.g., less than
10 micrometers). The amount of filler employed can range
for each of these additional components independently
from 0 to 100 phr, preferably from 5 to 50 phr.
Other components include thermoplastic polymers such
as (toughened) polystyrene, polypropene, ethene-vinyl
acetate and others. Polystyrene in particular is a common
additive to increase the hardness, albeit at the
detriment of the appearance.
Certain TPE compositions defined above are already
known, For instance, European patent application
No. 712,892 describes compositions comprising 1) one or
more block copolymers having at least two monoalkenyl
arene blocks (i.e., glassy blocks) separated by a
saturated conjugated diene block and II) a metallocene
polyolefin having a density from 0.86 to 0.91, and a
molecular weight distribution of less than 3. However,
TPE compositions comprising block copolymers wherein the
conjugated diene block still contains residual
unsaturation are believed to be novel. Accordingly, it is
a further embodiment to provide novel TPE compositions
that comprise:
(a) one or more styrenic block copolymers;
(b) -optionally- one or more ingredients selected from
extender oils, fillers, hardness regulators, flow
improvers, flex crack resistance improvers, stabilisers
vv stabilisers, pigments, blowing agents, and anti-
blocking agents; and
(c) one or more metallocene-based polyolefins of ethene
and from 8% to 30% by weight of an alpha-olefin comonomer
having from 3 to 20 carbon atoms, having a density from
0.86 to 0.91 and a molecular weight distribution (Mw/Mn
less than 3,10
20
25
PCT/EP00/09764
WO 01/2531 ~9-
with the proviso that component (a) is not a block
copolymer having at least two glassy blocks separated by
@ saturated conjugated diene block.
The definitions of the components of this novel TPE
Composition is similar to those given before, with the
exception of component (a), which excludes the
hydrogenated block copolymer known from European patent
application No. 712,892.
The TPE compositions for footwear applications may be
made by compounding the TPE with the other components
for instance using high-shear compounding equipment. on
an industrial scale, this is carried out on either a
batch mixer or continuous extrusion equipment. Use of co-
rotating twin screw extruders have proved to be
particularly suitable. Some typical mixing schemes and
conditions for the various types of mixing equipment used
in KRATON D compounding is disclosed in the
aforementioned Bulletin TPE 4.2.2, herewith incorporated
by reference.
Footwear in accordance with the present invention may
find use as soling material (outer, mid or in soles), as
clasps (ski-boots), heel counters and toe puffs. However
the TPE composition may also be used in adhesives or
other applications that require a uniform dull look.
Experimental
The following compound ingredients were used in the
examples:
“KRATON” D-4271 branched 50 phr oil-extended block
cs copolymer with 458 styrene content
and MFI of 10 (ex Shell)
TPS 476L hardener based on toughened
polystyrene with MEI of 5 (ex BASF
“PROCESS” KD 28 paraffinic extender oil (ex Shel)
“MILLICARE” 5 CaCo3 filler without surface10
15
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Wo 01/25331 PCTEPOO/09764
oo
treatment (ex OMYA)
“IRGANOX” 565 antioxidant (ex Ciba-Geigy:
Masterbatch sarmagum (ex Clariant
Black
“ENGAGE” 8150 metallocene polyolefin with MFI of 2
(ex DuPont Dow Elastomers)
“ENGAGE” 8585 metallocene polyolefin with MFI of 8
(ex DuPont Dow Elastomers)
“ENGAGE” 8440 metallocene polyolefin with MFI of 6
(ex DuPont Dow Elastomers)
MFI = melt flow index in g/10 min. at 190 °C/5 kg
(Tso 1133)
“KRATON”, “PROCESS”, “MILLICARB”, “IRGANOX” and “ENGAGE”
are trademarks.
TPE Compositions (“compounding”)
All solid ingredients, apart from the filler and
hardener which were added using a separate feeder, were
tumble mixed and subsequently dosed in a 40 mm, L/D = 27
co-rotating twin screw Betol extruder with gravimetric
feeding devices. The oil was injected directly into the
polymer melt. Extruded strands were water cooled and
granulated. 8 kg was prepared of each compound.
Injection moulding
Physical and flexural property test samples were
injection moulded on a 200 KN BATTENFELD BA 200/50 CD
injection moulding machine using exchangeable draw
moulds. Apart from the DIN abrasion test sample, the
mould cavity is film-gated over one side to give a well
defined flow pattern during moulding
Testing and physical properties
Dull look was assessed on the surface of 2 mm
injection moulded plates and visually ranked from very
dull (best), dull, semi-shiny to shiny (worst). DIN
Abrasion resistance was determined in accordance with the10
15
WO 01/2531 PCT/EPOO/09764
-u-
DIN 53516 method at 40 rpm, 10 N, 40 m. Shore A hardness
was determined after 30 seconds according to the ASTM
2240 method. Resilience was determined at 45° according
to the BS 903 AB method.
Results and discussion
All the results are reported in Tables 1 and 2.
Compositions 1 to 8 are made in accordance with the
present invention, whereas compositions A to D are not
Table 1 illustrates the suitability of metallocene
polyolefins (e.g., “ENGAGE” 8440) as replacement of
RB 830. When used in the same amount, similar appearance
is achieved, with a slight improvement on DIN Abrasion
when using the metallocene polyolefin
Compound D may have the best DIN Abrasion score, but
it also has the worst dull look. This is the result of
the presence of 20 phr hardener, instead of either
metallocene polyolefin of RB 830. If the hardener is
replaced by a metallocene polyolefin, then best results
are achieved with “ENGAGE” 8440.wo 0125331 PCT/EPOO/09T64
-12-
Table 1
compound 1] 2] 3]a B c
/KRATON” D 4271 100 [100 | 100 | 100 | 160 | i100
/ENGAGE” 8440, to | 20 | 30 | 0 0 0
RB 830 0 {0 |-0 | 10 | 20 30
res 476 L io | 10 | 10 | 10 | 10 10
OTL KD 28 20 | 20 | 20 | 20 | 20 20
cacd3 is} is | is | is | 15 15
/SIRGANOX” 565 Oifotfoi;oa [01] 014
IMB BLACK 7 )a]d T T 1
Density (kg/1) 0.97/1.01/1.01] 1.01 | 1.01] 1.01
Hardness Shore A | 64 | 64 | 70 | 60 | 65 68
Din Abrasion (mm3)| 235 | 255 | 260 | 245 | 260 | 260
Resilience (%) 43 [46 | 46 | 49 | 49 52
Dall Look* s7s[s/s| D | D S s
* VD = Very Dull, D = Dull, S/S = Semi Shiny, S = ShinyWo 0125331 ce PCT/EP00/09764
ble 2
lcompounp ales 6 D 1 8
PKRATON” D 4271 100 [100 [100 | i100 | 100 100
ENGAGE” 6150 0 0 Oye lee20) 0
ENGAGE” 6585 Oo 0 0 0 20
ENGAGE” 6440, 10 [20 | 30 | 0 0 0
TPS 476 L Oealgo: 0 [20] 0 0
OTL KD 28 20 [20 | 20 | 20 | 20 20
caco3 is [as fis [is | is 15
/ERGANOX” 565 (ode [025 | mO= a [oma 0.1
[MB BLACK T fa T I a T
Density (kg/1) 1 [i-00[ 1 /t.00/ 0.58] 0.98
Hardness Shore A | 62 | 65 | 70 | 59 | 5a 64
Din Abrasion (mm3)| 260 | 260] 230 | 203] 353 340
Resilience (#) a [as | 43 [49] 46 a6
Dull Look* VD e/a VDE geiper les D S75
* VD = Very Dull, D = Dull, S/S = Semi Shiny, S =
Shiny10
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Wo 01/25331 PCT/EPOO/09764
-14-
CLAIMS
1. Footwear made from a thermoplastic elastomer
composition comprising
(a) one or more styrenic block copolymers;
(b) -optionally- one or more ingredients selected from
extender oils, fillers, hardness regulators, flow
improvers, flex crack resistance improvers, stabilisers
Uv stabilisers, pigments, blowing agents, and anti-
blocking agents; and
(c) one or more metallocene-based polyolefins of ethene
and from 8% to 40% by weight of an alpha-olefin comonomer
having from 3 to 20 carbon atoms, having a density from
0.86 to 0.95 kg/1 and a molecular weight distribution
(Mw/Min) less than 3.
2. Footwear as claimed in any of the preceding claims
wherein component (a) comprises a branched block
copolymer or a mixture of a branched block copolymer and
a linear block copolymer.
3. Footwear as claimed in any of the preceding claims
wherein component (a) comprises an (SB)nX, (SI) nX, SB,
SI, SBS and/or SIS block copolymer, and/or a hydrogenated
version thereof.
4, Footwear as claimed in any of the preceding claims
wherein component (c) comprises a metallocene-based
polyolefin of ethene and an alpha-olefin comonomer having
from 4 to 12 carbon atoms.
5. Footwear as claimed in claim 4, wherein component (c
comprises a metallocene-based polyolefin the density of
which varies from 0.86 to 0.95 kg/l, preferably from 0.88
to 0.92 kg/l, more preferably from 0.89 to 0.90 kg/l.
6. Footwear as claimed in claim 5, wherein component (c:
comprises a metallocene-based polyolefin having a density
of 0.868 kg/1 and an MFI 2 g/10 min; a density 0.885 kg/110
1s
20
wo 01/25331 PCTIEPO0/09764
- 15 -
and an MFI 8 g/10 min; or a density of 0.897 kg/l and an
MFI of 6 g/10 min.
7. Footwear as claimed in any of the preceding claims
wherein component (c) is present in an amount of from 5
to 35 parts by weight per 100 parts by weight of
component (a) (phr), preferably in an amount of from 10
to 30 phr, most preferably at around 20 phr.
8. A thermoplastic elastomer composition comprising
(a) one or more styrenic block copolymers;
(b) -optionally- one or more ingredients selected from
extender oils, fillers, hardness regulators, flow
improvers, flex crack resistance improvers, stabilisers,
UV stabilisers, pigments, blowing agents, and anti-
blocking agents; and
(c) one or more metallocene-based polyolefins of ethene
and from 8% to 30% by weight of an alpha-olefin comonomer
having from 3 to 20 carbon atoms, having a density from
0.86 to 0.91 kg/1 and a molecular weight distribution
(Mw/Mn) less than 3, with the proviso that component (a
is not a block copolymer having at least two glassy
blocks separated by a saturated conjugated diene block.
9. A process for compounding the thermoplastic elastomer
composition of claim 1 or 7, by compounding the
components using high-shear compounding equipment.‘TERNATIONAL SEARCH REPORT [in avona appication no
PCT/EP 00/09764
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EPO-Internal, WPI Data, PAJ
( DOCUNENTS CONSIDERED TO BE RELEVANT
‘Galego | Okaton of document wth ination, where prope, o he rekvan paseagee eievantto cam No
x EP 0 845 498 A (RIKEN VINYL IND) 1-5,7-9
3 dune 1998 (1998-06-03)
* page 1, line 12 ; page 3, line 45 - page
4, line 22 ; page 4, line 55 ~ page 5,
line 33 ; claims 1-8 ; abstract =
page 7, line 23-28
x WO 95 33006 A (DOW CHEMICAL CO) 1-8
7 December 1995 (1995-12-07)
+ page 26, line 2-3 ;claims 1-11,14-18 ;
page 9, line 26 -page 10, line 3 ;page 10,
line 25 -page 11, line 7’ ;abstract ; page
13, line 26 -page 14, line 25 ;page 20,
Tine 10-12 ;pg 28 Table +
] Fer documents ar sean he contruatan of ox Fx] Paentamey momers ar stain annex.
Sposa calogones of cies tar “7 Intor document published ater te internation ng date
‘roy dat and notin zone wane appleaion Bat
cam ing te general stat ofthe a whieh not Elgde understand the panel o neo anon
‘onnoredto be parca rovance
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irthan me prs aa cre
‘Canna bo consdered novel or cant be coneeted
IrveWe an ion stop whon ne cocaine thon ne
“7 cocumant of panic etevance: te clara invention
annus creado moe anrine Spon he
tren such canatneton beg obvious io = Person sid
4° document member fhe same patent tary
‘ate oe atl compan a arn] Sara
‘Date a mang oho rarabonal earch oper
1 February 2001 08/02/2001
Teaaeangaared tok cece
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geen Hammond, A
Foes POTROVEO oan oa)
page 1 of 2INTERNATIONAL SEARCH REPORT
th ational Application Wo
PCT/EP 00/09764
‘7 Continaationy OOCUMENTS CONSIDERED TO BE RELEVANT
Tateann” | Chat a aocument wih ndcatan Aner RODRIG TRS OAN PIS Fasrantocam te
x US 5 847 051 A (HWO CHARLES CHIU-HSIUNG 8,9
ET AL) 8 December 1998 (1998-12-08)
y * claims 6,7 ; column 4, line 57 - column 1-7
6, line 35 ; column 6, line 58 - column 7,
Vine 7 ; abstract ; column 2, line 58-59 +
column 2, Tine 43-46
y EP 0 770 645 A (RIKEN VINYL IND) 17
2 May 1997 (1997-05-02)
* page 2, line 12 ; page 5, line 34-40 +
page 4, line 23 -page 5, line 9; claims
1-20
A US 4 216 131 A (HIMES GLENN R ET AL) 1-9
5 August 1980 (1980-08-05)
* column 1, line 38-58 ; column 2, line
21-48 ; column 3, line 1-22 ; claims 1-10+
column 3, line 61 column 4, line 24
A WO 95 27756 A (ESPOSITO ANTHONY S JR ) 19
sANDERSON MICHAEL C (US)) |
19 October 1995 (1995-10-19)
* claims 1-12 ; page 8, line 18 - page 10,
line 28 +
page 2, line 3-6
A US 4 225 500 A (NEWTON JR CHARLES 6) 1-9
30 September 1980 (1980-09-30)
* column 1, line 58 - column 3, line 17 +
column 1, line 1-12
Fas RSE conan oss en Da TR
page 2 of 2INTERNATIONAL SEARCH REPORT
Information on patent family members
‘ational Application No
PCT/EP_00/09764
Patent cocument Publication Patent family Publieaton
coed in search report ate | member(s), ose
EP 0845498 A 03-06-1998 UP 10158465 A 16-06-1998
oP 3102851 B 23-10-2000
JP 10251480 A 22-09-1998
EP 0994153 A 19-04-2000
Wo 9533006 A. 07-12-1995 AU 2815895 A 21-12-1995
AU 3509899 A 19-08-1999
BR 9507907 A 16-09-1997
CA 2191470 A 07-12-1995
CN 1151750 A 11-06-1997
OE 69511699 D 30-09-1999
DE 69511699 T 23-12-1999
EP 0767814 A 16-04-1997
ES 2135750 T 01-11-1999
YP 10501285 T 03-02-1998
Us 5847051 A 08-12-1998 NONE
EP 0770645 A 02-05-1997 oP 3102842 B 23-10-2000
OP 8225713 A 03-09-1996
oP 3102844 B 23-10-2000
JP 9151295 A 10-06-1997
JP 3102847 B 23-10-2000
JP 9278979 A 28-10-1997
DE 69606489 D 09-03-2000
DE 69606489 T 21-09-2000
Us 6048933 A 11-04-2000
Us 5929165 A 27-07-1999
Us 4216131 A
WO 9527756 A
05-08-1980
2280095
19-10-1995
AU
30-09-1980
us 4225500 A AU
cA
5716980
1137684
30-10-1995
09-10-1980
14-12-1982
A
A
Fem POTIEARTO baton mn ay)