Field of the invention
[0001] The present application relates to a woven fabric comprising a yarn, said yarn in
turn comprising filaments comprising a metallocene polypropylene. Further, the present
application relates to articles comprising such a woven fabric. In addition, the present
application relates to a process for the production of such woven fabric and to a
process for the production of such articles comprising said woven fabric.
The technical problem and the prior art
[0002] Due to good mechanical and chemical properties in combination with good economics
polypropylene has become the material of choice for a large number of applications,
such as injection-molded cups and containers, biaxially oriented films (BOPP) and
spunbonded nonwovens.
[0003] Polypropylene has also been used in a number of applications, wherein fibers or yarns
were used to produce woven fabrics. Such woven fabrics in turn have been used for
example in undergarments or in bags and sacks for the transport and storage of bulk
goods.
[0004] For environmental reasons industry is more and more interested in reducing the weight
of the woven fabric. There is therefore a need for improved woven fabrics, preferably
with the added benefit of easier production of such woven fabrics.
[0005] Thus, it is an object of the present application to provide a woven fabric that has
improved properties.
[0006] Particularly, it is an object of the present application to provide a woven fabric
that has the same mechanical properties, such as for example tensile strength or elongation
at yield or break, at lower weight than a conventional woven fabric.
[0007] It is a further object of the present application to provide a yarn for use in the
production of a woven fabric, said yarn being easily produced.
Brief description of the invention
[0008] Any of the above objects may be achieved either alone or in combination by the woven
fabric disclosed in the present application.
[0009] Thus, the present application provides the woven fabric, which comprises yarn, said
yarn in turn comprising filaments, said filaments in turn comprising a component A,
said component A comprising a metallocene polypropylene
[0010] Further, the present application provides an article comprising said woven fabric.
[0011] Additionally, the present application provides a process for producing such woven
fabric and a process for producing an article comprising such woven fabric.
Detailed description of the invention
[0012] Throughout the present application the terms "polypropylene" and "propylene polymer"
may be used synonymously.
[0013] Throughout the present application the melt flow index of polypropylene and polypropylene
compositions is determined according to ISO 1133, condition L, at 230°C and 2.16 kg.
[0014] Throughout the present application the melt index of polyethylene and polyethylene
compositions is determined according to ISO 1133, condition D, at a temperature of
190°C and a load of 2.16 kg.
[0015] The present inventors have found that a woven fabric, which comprises a yarn, said
yarn in turn comprising filaments, said filaments in turn comprising a component A,
said component A comprising a metallocene polypropylene can fulfill at least one of
the above-mentioned objectives.
[0016] Preferably the filaments comprise a further component B, which covers at least 50
% of the surface of said filaments, more preferably at least 70 % or 80 %, even more
preferably at least 90 % or 95 %, still even more preferably at least 99%, and most
preferably component B covers the entire surface of the filaments, said component
B comprising a metallocene polyethylene.
[0017] It is preferred that component A comprises at least 50 wt%, relative to the total
weight of component A, of a metallocene polypropylene, more preferably of at least
75 wt% or 90 wt%, even more preferably of at least 95 wt% or 97 wt%, and still even
more preferably of at least 99 wt%. Most preferably, component A consists of the metallocene
polypropylene.
[0018] Component B preferably comprises at least 50 wt%, relative to the total weight of
component B, of a metallocene polyethylene, more preferably of at least 75 wt% or
90 wt%, even more preferably of at least 95 wt% or 97 wt%, and still even more preferably
of at least 99 wt%. Most preferably, component B consists of a metallocene polyethylene.
[0019] By the terms "metallocene polypropylene" and "metallocene polyethylene", which in
the following may also simply be referred to as "polypropylene" resp. "polyethylene",
it is meant that the polypropylene resp. the polyethylene has been produced with a
metallocene-based polymerization catalyst. The use of such a specific polymerization
catalyst will also impart characteristics to the polypropylene resp. the polyethylene
that clearly distinguish it from polypropylenes resp. polyethylenes produced with
other types of polymerization catalysts, such as for example Ziegler-Natta polymerization
catalysts, and in consequence also result in different processing behavior as well
as different properties of the final article produced therewith.
POLYPROPYLENE
[0020] The polypropylene used herein preferably has a melt flow index of at least 5 dg/min,
more preferably of at least 7 dg/min and most preferably of at least 10 dg/min. The
polypropylene used herein preferably has a melt flow index of at most 100 dg/min,
more preferably of at most 75 dg/min, even more preferably of at most 50 dg/min, still
even more preferably of at most 40 dg/min, and most preferably of at most 30 dg/min.
[0021] Preferably, the polypropylene used herein has a molecular weight distribution (MWD),
defined as M
w/M
n, i.e. the ratio of weight average molecular weight M
w over number average molecular weight M
n, of at least 1.0, more preferably of at least 1.5 and most preferably of at least
2.0. Preferably, the polypropylene used herein has a molecular weight distribution,
defined as M
w/M
n, of at most 4.0, more preferably of at most 3.5, even more preferably of at most
3.0, and most preferably of at most 2.5. Molecular weights can be determined by size
exclusion chromatography (SEC) as described in the examples.
[0022] Preferably, the polypropylene used herein is characterized by high isotacticity,
for which the content of mmmm pentads is a measure. Preferably, the content of mmmm
pentads is at least 90 %, more preferably at least 95 %, and most preferably at least
97 %. Isotacticity may be determined by
13C-NMR analysis as described in the test methods.
[0023] Preferably, the polypropylene used herein is characterized by a low content of xylene
solubles. Preferably, the polypropylene used herein has at most 3.0 wt% of xylene
solubles, relative to the total weight of the polypropylene, more preferably at most
2.5 wt% and most preferably at most 2.0 wt%.
[0024] The polypropylene used herein preferably is a propylene homopolymer or a random copolymer
of propylene and up 6.0 wt% of at least one comonomer, relative to the total weight
of said random copolymer, though propylene homopolymer is preferred. The preferred
random copolymer is a random copolymer of propylene and up to 5.0 wt%, more preferably
up to 4.5 wt%, and most preferably up to 4.0 wt% of at least one comonomer, relative
to the total weight of said random copolymer. The comonomer is different from propylene
and preferably is an α-olefin having from one to 10 carbon atoms. Examples of suitable
α-olefins are ethylene, butene-1, pentene-1, hexene-1, octene-1 and 3-methyl-pentene-1.
The preferred comonomers are ethylene and butene-1. The most preferred comonomer is
ethylene.
[0025] Preferably, the polypropylene used herein is characterized by a melting temperature
T
melt of at most 160°C. The determination of melting temperatures is generally done by
first heating to a temperature above the melting temperature, e.g. to 200°C, and keeping
the sample at this temperature for a certain time, e.g. for 3 minutes, so as to erase
the thermal history of the sample. After cooling the sample is then reheated for the
measurement of the melting temperature. For the determination of the melting temperature
T
melt the heating and cooling rate used herein is 20°C/min.
[0026] Preferably, the polypropylene used herein is characterized by a percentage of 2,1-insertions
relative to the total number of propylene molecules in the polymer chain of at least
0.1 %. Preferably, the percentage of 2,1-insertions is at most 1.5 %, more preferably
at most 1.3 %, even more preferably at most 1.2 %, still even more preferably at most
1.1 %, and most preferably at most 1.0 %. A detailed description on the determination
of the percentage of 2,1-insertions is given in the description of the examples.
[0027] The polypropylene used herein may also comprise further additives, such as by way
of example, antioxidants, light stabilizers, acid scavengers, lubricants, antistatic
additives, and colorants. An overview of such additives may be found in
Plastics Additives Handbook, ed. H. Zweifel, 5th edition, 2001, Hanser Publishers.
[0028] The polypropylene used herein is a metallocene polypropylene, i.e. it is produced
with a metallocene-based polymerization catalyst, with the metallocene-based polymerization
catalyst comprising a bridged metallocene component, a support and an activating agent.
Such metallocene-based polymerization catalysts are generally known in the art and
need not be explained in detail.
[0029] The metallocene component can be described by the following general formula
(µ-R
a)(R
b)(R
c)MX
1X
2 (I)
wherein R
a, R
b, R
c, M, X
1 and X
2 are as defined below.
R
a is the bridge between R
b and R
c, i.e. R
a is chemically connected to R
b and R
c, and is selected from the group consisting of ―(CR
1R
2)
p―, ―(SiR
1R
2)
p―, ― (GeR
1R
2)
p―, ―(NR
1)
p―, ―(PR
1)
p―, ―(N
+R
1R
2)
p― and ―(P
+R
1R
2)
p―, and p is 1 or 2, and wherein R
1 and R
2 are each independently selected from the group consisting of hydrogen, C
1-C
10 alkyl, C
5-C
8 cycloalkyl, C
6-C
15 aryl, alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl, or any two neighboring R may form a cyclic saturated or non-saturated C
4-C
10 ring; each R
1 and R
2 may in turn be substituted in the same way. Preferably R
a is ―(CR
1R
2)
p― or ―(SiR
1R
2)
p― with R
1, R
2 and p as defined above. Most preferably R
a is ―(SiR
1R
2)
p― with R
1, R
2 and p as defined above. Specific examples of R
a include Me
2C, ethanediyl (-CH
2-CH
2-), Ph
2C and Me
2Si.
[0030] M is a metal selected from Ti, Zr and Hf, preferably it is Zr.
[0031] X
1 and X
2 are independently selected from the group consisting of halogen, hydrogen, C
1-C
10 alkyl, C
6-C
15 aryl, alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl. Preferably X
1 and X
2 are halogen or methyl.
[0032] R
b and R
c are selected independently from one another and comprise a cyclopentadienyl ring.
[0033] Preferred examples of halogen are Cl, Br, and I. Preferred examples of C
1-C
10 alkyl are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl.
Preferred examples of C
5-C
7 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferred examples
of C
6-C
15 aryl are phenyl and indenyl. Preferred examples of alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl are benzyl (-CH
2-Ph), and -(CH
2)
2-Ph.
[0034] Preferably, R
b and R
c may both be substituted cyclopentadienyl, or may be independently from one another
unsubstituted or substituted indenyl or tetrahydroindenyl, or R
b may be a substituted cyclopentadienyl and R
c a substituted or unsubstituted fluorenyl. More preferably, R
b and R
c may both be the same and may be selected from the group consisting of substituted
cyclopentadienyl, unsubstituted indenyl, substituted indenyl, unsubstituted tetrahydroindenyl
and substituted tetrahydroindenyl. By "unsubstituted" is meant that all positions
on R
b resp. R
c, except for the one to which the bridge is attached, are occupied by hydrogen. By
"substituted" is meant that, in addition to the position at which the bridge is attached,
at least one position on R
b resp. R
c is occupied by a substituent other than hydrogen.
[0035] A substituted cyclopentadienyl may for example be represented by the general formula
C
5R
3R
4R
5R
6. A substituted indenyl may for example be represented by the general formula C
9R
7R
8R
9R
10R
11R
12R
13R
14. A substituted 4,5,6,7-tetrahydroindenyl may for example be represented by the general
formula C
9H
8R
15R
16R
17R
18. A substituted fluorenyl may for example be represented by the general formula C
13R
19R
20R
21R
22R
23R
24R
25R
26. Each of the substituents R
3 to R
26 may be independently selected from the group consisting of hydrogen, C
1-C
10 alkyl, C
5-C
7 cycloalkyl, C
6-C
15 aryl, and alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl, or any two neighboring R may form a cyclic saturated or non-saturated C
4-C
10 ring; provided, however, that not all substituents simultaneously are hydrogen.
[0036] Preferred metallocene components are those having C
2-symmetry or those having C
1-symmetry. Most preferred are those having C
2-symmetry.
[0037] Particularly suitable metallocene components are those wherein R
b and R
c are the same and are substituted cyclopentadienyl, preferably wherein the cyclopentadienyl
is substituted in the 2-position, the 3-position, or simultaneously the 2-position
and the 3-position.
[0038] Particularly suitable metallocene components are also those wherein R
b and R
c are the same and are selected from the group consisting of unsubstituted indenyl,
unsubstituted tetrahydroindenyl, substituted indenyl and substituted tetrahydroindenyl.
Substituted indenyl is preferably substituted in the 2-position, the 3-position, the
4-position, the 5-position or any combination of these, more preferably in the 2-position,
the 4-position or simultaneously in the 2-position and the 4-position. Substituted
tetrahydroindenyl is preferably substituted in the 2-position, the 3-position, or
simultaneously the 2-position and the 3-position.
[0039] Particularly suitable metallocene components may also be those wherein R
b is a substituted cyclopentadienyl and R
c is a substituted or unsubstituted fluorenyl. The substituted cyclopentadienyl is
preferably substituted in the 2-position, the 3-position, the 5-position or simultaneously
any combination of these, more preferably in the 3-position or the 5-position or both
simultaneously, most preferably in the 3-position only, with a bulky substituent.
Said bulky substituent may for example be -CR
27R
28R
29 or -SiR
27R
28R
29 with R
27, R
28 and R
29 independently selected from group consisting of C
1-C
10 alkyl, C
5-C
7 cycloalkyl, C
6-C
15 aryl, and alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl, or any two neighboring R may form a cyclic saturated or non-saturated C
4-C
10 ring. it is preferred that R
27, R
28 and R
29 are methyl.
[0040] Examples of particularly suitable metallocenes are:
dimethylsilanediyl-bis(2-methyl-cyclopentadienyl)zirconium dichloride,
dimethylsilanediyl-bis(3-methyl-cyclopentadienyl)zirconium dichloride,
dimethylsilanediyl-bis(3-tert-butyl-cyclopentadienyl)zirconium dichloride,
dimethylsilanediyl-bis(3-tert-butyl-5-methyl-cyclopentadienyl)zirconium dichloride,
dimethylsilanediyl-bis(2,4-dimethyl-cyclopentadienyl)zirconium dichloride,
dimethylsilanediyl-bis(indenyl)zirconium dichloride,
dimethylsilanediyl-bis(2-methyl-indenyl)zirconium dichloride,
dimethylsilanediyl-bis(3-methyl-indenyl)zirconium dichloride,
dimethylsilanediyl-bis(3-tert-butyl-indenyl)zirconium dichloride,
dimethylsilanediyl-bis(4,7-dimethyl-indenyl)zirconium dichloride,
dimethylsilanediyl-bis(tetrahydroindenyl)zirconium dichloride,
dimethylsilanediyl-bis(benzindenyl)zirconium dichloride,
dimethylsilanediyl-bis(3,3'-2-methyl-benzindenyl)zirconium dichloride,
dimethylsilanediyl-bis(4-phenyl-indenyl)zirconium dichloride,
ethanediyl-bis(indenyl)zirconium dichloride,
ethanediyl -bis(tetrahydroindenyl)zirconium dichloride,
isopropylidene-(3-tert-butyl-cyclopentadienyl)(fluorenyl) zirconium dichloride
isopropylidene-(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl) zirconium dichloride.
[0041] The metallocene may be supported according to any method known in the art. In the
event it is supported, the support used herein may be any organic or inorganic solid,
particularly porous supports such as talc, inorganic oxides, and resinous support
material such as polyolefin. Preferably, the support material is an inorganic oxide
in its finely divided form.
[0042] The polymerization of propylene and one or more comonomers in presence of a metallocene-based
catalytic system can be carried out according to known techniques in one or more polymerization
reactors. The metallocene polypropylene used in the present invention is preferably
produced by polymerization in liquid propylene at temperatures in the range from 20°C
to 100°C. Preferably, temperatures are in the range from 60°C to 80°C. The pressure
can be atmospheric or higher. It is preferably between 25 and 50 bar. The molecular
weight of the polymer chains, and in consequence the melt flow of the metallocene
polypropylene, is regulated by the addition of hydrogen to the polymerization medium.
POLYETHYLENE
[0043] The polyethylene preferably is a homopolymer of ethylene or a copolymer of ethylene
and at least one comonomer, said comonomer being a C
3 to C
10 alpha-olefin, such as 1-butene, 1-pentene, 1-hexene, 1-octene, 1-methylpentene, with
1-butene and 1-hexene being the preferred comonomers and 1-hexene being the most preferred
comonomer.
[0044] Preferably, the polyethylene used herein has a molecular weight distribution (MWD),
defined as M
w/M
n, in the range from 2 to 7, and most preferably in the range from from 2 to 5. Molecular
weights can be determined by size exclusion chromatography (SEC) as described in the
examples.
[0045] Preferably, the polyethylene has a melt index in the range of at least 1 dg/min,
preferably of at least 5 dg/min, even more preferably of at least 7 dg/min, still
even more preferably at least 10 dg/min, and most preferably of at least 20 dg/min.
Preferably, the polyethylene has a melt index of at most 150 dg/min, more preferably
of at most 100 dg/min, even more preferably of at most 75 dg/min and most preferably
of at most 50 dg/min.
[0046] Preferably, the polyethylene has a density of at least 0.920 g/cm
3, more preferably of at least 0.925 g/cm
3, even more preferably of at least 0.927 g/cm
3, still even more preferably of at least 0.930 g/cm
3, and most preferably of at least 0.932 g/cm
3. It has a density of at most 0.965 g/cm
3, preferably of at most 0.955 g/cm
3, more preferably of at most 0.950 g/cm
3, even more preferably of at most 0.945 g/cm
3, and most preferably of at most 0.940 g/cm
3. The density is measured at 23°C following the method described in ASTM D 1505.
[0047] The polyethylene used herein is a metallocene polyethylene, i.e. it is a polyethylene
produced with a metallocene-based polymerization catalyst, with the metallocene-based
polymerization catalyst comprising a metallocene component, a support and an activating
agent. Such metallocene-based polymerization catalysts are generally known in the
art and need not be explained in detail.
[0048] The metallocene component can be described by the following general formula
(µ-R
a)
n(R
b)(R
c)MX
1X
2 (II)
wherein
n = 0 or 1, and R
a is the bridge, i.e. n = 1, between R
b and R
c, i.e. R
a is chemically connected to R
b and R
c, and is selected from the group consisting of ―(CR
1R
2)
p―, ―(SiR
1R
2)
p―, ―(GeR
1R
2)
p―, ―(NR
1)
p―, ―(PR
1)
p―, ―(N
+R
1R
2)
p― and ― (P
+R
1R
2)
p―, and p is 1 or 2, and wherein R
1 and R
2 are each independently selected from the group consisting of hydrogen, C
1-C
10 alkyl, C
5-C
8 cycloalkyl, C
6-C
15 aryl, alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl, or any two neighboring R may form a cyclic saturated or non-saturated C
4-C
10 ring; each R
1 and R
2 may in turn be substituted in the same way. Preferably R
a is ―(CR
1R
2)
p― or ― (SiR
1R
2)
p― with R
1, R
2 and p as defined above. Most preferably R
a is ― (CR
1R
2)p― with R
1, R
2 and p as defined above. Specific examples of R
a include Me
2C, ethanediyl (-CH
2-CH
2-), Ph
2C and Me
2Si.
[0049] M is a metal selected from Ti, Zr and Hf, preferably it is Zr.
[0050] X
1 and X
2 are independently selected from the group consisting of halogen, hydrogen, C
1-C
10 alkyl, C
6-C
15 aryl, alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl. Preferably X
1 and X
2 are halogen or methyl.
[0051] R
b and R
c are selected independently from one another and comprise a cyclopentadienyl ring.
[0052] Preferred examples of halogen are Cl, Br, and I. Preferred examples of C
1-C
10 alkyl are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, and tert-butyl.
Preferred examples of C
5-C
7 cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Preferred examples
of C
6-C
15 aryl are phenyl and indenyl. Preferred examples of alkylaryl with C
1-C
10 alkyl and C
6-C
15 aryl are benzyl (-CH
2-Ph), and -(CH
2)
2-Ph.
[0053] It is, however, preferred to use a metallocene component of the following general
formula, wherein
- n is 1;
- Ra is ―(CR1R2)p― or ―(SiR1R2)p―, most preferably Ra is ―(CR1R2)p― with R1, R2 and p as defined above;
- M is a metal selected from Ti, Zr and Hf, preferably it is Zr;
- X1 and X2 are the same and are halogen or methyl, preferably chlorine or methyl, and most preferably
chlorine; and
- Rb and Rc are selected independently from one another and comprise an indenyl or tetrahydroindenyl.
[0054] Preferably, the indenyl or tetrahydroindenyl, if substituted, is symmetrically substituted
in positions 2 and/or 4, and more preferably they are unsubstituted.
[0055] Examples of particularly suitable metallocene components include the following: bis(n-butylcyclopentadienyl)zirconium
dichloride,
ethanediyl-bis(1-indenyl)zirconium dichloride,
ethanediyl-bis(2-methyl-1-indenyl)zirconium dichloride,
ethanediyl-bis(4-methyl-1-indenyl)zirconium dichloride,
ethanediyl-bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride.
[0056] The polymerization of ethylene and optionally one or more comonomers in presence
of a metallocene-based polymerization catalyst can be carried out according to known
techniques in one or more polymerization reactors. The metallocene polyethylene used
herein is preferably produced by polymerization in a liquid diluent, which is inert
under polymerization conditions, such as an alkane, at temperatures in the range from
20°C to 100°C. Preferably, temperatures are in the range from 60°C to 80°C. The pressure
can be atmospheric or higher. It is preferably between 25 and 50 bar. The molecular
weight of the polymer chains, and in consequence the melt index of the metallocene
polyethylene, is controlled by the addition of hydrogen to the polymerization medium.
YARN AND WOVEN FABRIC
[0057] The yarn comprising filaments, said filaments in turn comprising a component A as
defined above, is produced by commonly known production methods, such as for example
described in
Polypropylene Handbook, ed. Nello Pasquini, 2nd edition, Hanser, 2005, pages 397-403, by
- (a) providing a polymer blend comprising a metallocene polypropylene,
- (b) feeding the polymer blend of step (a) to an extruder,
- (c) subsequently melt-extruding the polymer blend to obtain a molten polymer stream,
- (d) extruding the molten polymer stream of step (c) from a number of fine capillaries
of a spinneret, thus obtaining filaments of molten polymer,
- (e) cooling the filaments obtained in step (d) to form solidified filaments, and
- (f) combining a number of the solidified filaments of step (e) to form a yarn.
[0058] Generally, a polymer blend comprising a metallocene polypropylene as defined above
is provided, and then fed to an extruder. In the extruder the polymer blend is melt-extruded,
i.e. extruded at a temperature above its melting temperature, thus obtaining a molten
polymer stream. Preferably, the melt-extrusion is done at a temperature of the molten
polymer blend in the range from 200 °C to 300 °C, more preferably in the range from
220 °C to 280 °C. Subsequently, the molten polymer stream is extruded from a number
of fine capillaries of a spinneret, thus obtaining filaments of molten polymer. Alternatively,
the molten polymer stream may pass through a manifold to direct the flow of molten
polymer stream to more than one spinneret, for example to between 4 and 20 spinnerets.
Optionally, the molten polymer stream may pass through a gear pump and/or a filter
pack before each spinneret. Each spinneret has a number, preferably from 20 to 500,
of fine capillaries, which for example may have a diameter from 0.2 mm to 1.0 mm..
The capillaries may be for example circular, triangular, trilobal, tetralobal, or
cross-shaped. the filaments of molten polymer are cooled to form solidified filaments,
which may optionally be drawn. A number of solidified filaments is then combined to
form a yarn. Preferably, the solidified filaments obtained in step (e) have a titer
in the range from 1 dtex to 100 dtex, preferably from 2 dtex to 90 dtex and most preferably
from 5 dtex to 80 dtex. A number of filaments is combined to form a yarn.
[0059] Preferably, the yarn has a titer in the range from 10 dtex to 2000 dtex. For some
applications the yarn might even have an even higher denier. Spinning speeds, i.e.
the speed at which the solidified filaments are withdrawn before any optional drawing,
may for example be in the range from 300 m/min to 6000 m/min.
[0060] The production of the yarn comprising filaments, said filaments in turn comprising
a component A and a component B as defined above are produced by
(a1) providing a first polymer blend comprising a metallocene polypropylene,
(a2) providing a second polymer blend comprising a metallocene polyethylene,
(b1) providing the first polymer blend of step (a1) to a first extruder,
(b2) providing the second polymer blend of step (a2) to a second extruder,
(c1) melt-extruding the first polymer blend of step (a1) through a number of fine
capillaries of a spinneret,
(c2) melt-extruding the second polymer blend of step (a2) through a number of fine
openings surrounding said capillaries of step (c1),
(d) combining the extrudates of steps (c1) and (c2) to form single filaments of molten
polymer,
(e) cooling the filaments obtained in step (d) to form solidified filaments, and
(f) combining a number of solidified filaments of step (e) to form a yarn.
[0061] In a further step the yarn is used to produce the woven fabric by weaving methods
well-known to the person skilled in the art.
[0062] The woven fabrics described above are characterized by improved mechanical properties,
such as increased tensile strength and elongation, with respect to woven fabrics of
the same basis weight produced with yarns of the same specifications, i.e. same number
of filaments and same titer. In addition, these woven fabrics show increased cohesion
of the woven fabric under changing load, i.e. they have an increased life time, for
example when used as sacks and bags. Additionally, the yarns used in the production
of the woven fabric can be produced at higher spinning speeds, thus rendering their
production more economic. The woven fabrics as described herein are also characterized
by lower volatiles content and by lower extractibles content.
[0063] Woven fabrics comprising filaments, which in turn comprise a component A and a component
B as defined above, are also found to have superior softness as well as improved UV-stability.
In addition, the filaments, and in consequence the yarn and woven fabrics, show reduced
abrasion and thus can be more easily processed.
[0064] The woven fabric in turn is used to produce articles such as for examples bags and
sacks of various sizes; nets and netting, such as for example fishing nets or anti-insect
netting (commonly also referred to as "mosquito nets"); clothing, such as undergarments,
socks, liners, sportswear; drapes; woven belts and straps, such as lifting straps;
and upholstery for furniture and car seats.
Examples
TEST METHODS
[0065] Melt flow index of polypropylene and polypropylene compositions is determined according
to ISO 1133, condition L, at 230°C and 2.16 kg.
[0066] Molecular weights are determined by Size Exclusion Chromatography (SEC) at high temperature
(145°C). A 10 mg PP sample is dissolved at 160°C in 10 ml of trichlorobenzene (technical
grade) for 1 hour. Analytical conditions for the GPCV 2000 from WATERS are :
- Injection volume: +/- 400 µl
- Concentration of injected sample: 1 mg ml-1
- Automatic sample preparation and injector temperature: 160°C
- Column temperature: 145°C
- Detector temperature: 160°C
- Column set: 2 Shodex AT-806MS and 1 Styragel HT6E
- Flow rate: 1 ml/min
- Detector: Infrared detector (2800-3000 cm-1)
- Calibration: Narrow standards of polystyrene (commercially available)
- Calculation for polypropylene: Based on Mark-Houwink relation (log10(MPP) = log10(MPS) ― 0.25323); cut off on the low molecular weight end at MPP = 1000.
- Calculation for polyethylene: Based on Mark-Houwink relation (log10(MPE) = 0.965909 · log10(MPS) ― 0.28264); cut off on the low molecular weight end at MPE = 1000.
[0067] The molecular weight distribution (MWD) is then calculated as M
w/M
n.
[0068] Xylene solubles (XS), i.e. the xylene soluble fraction, are determined as follows:
Between 4.5 and 5.5 g of propylene polymer are weighed into a flask and 300 ml xylene
are added. The xylene is heated under stirring to reflux for 45 minutes. Stirring
is continued for 15 minutes exactly without heating. The flask is then placed in a
thermostat bath set to 25°C +/- 1°C for 1 hour. The solution is filtered through Whatman
n° 4 filter paper and exactly 100 ml of solvent are collected. The solvent is then
evaporated and the residue dried and weighed. The percentage of xylene solubles ("XS"),
i.e. the amount of the xylene soluble fraction, is then calculated according to
XS (in wt%) = (Weight of the residue / Initial total weight of PP) * 300 with all
weights being in the same unit, such as for example in grams.
[0069] The
13C-NMR analysis is performed using a 400 MHz Bruker NMR spectrometer under conditions
such that the signal intensity in the spectrum is directly proportional to the total
number of contributing carbon atoms in the sample. Such conditions are well known
to the skilled person and include for example sufficient relaxation time etc. In practice
the intensity of a signal is obtained from its integral, i.e. the corresponding area.
The data is acquired using proton decoupling, 4000 scans per spectrum, a pulse repetition
delay of 20 seconds and a spectral width of 26000 Hz. The sample is prepared by dissolving
a sufficient amount of polymer in 1,2,4-trichlorobenzene (TCB, 99%, spectroscopic
grade) at 130°C and occasional agitation to homogenize the sample, followed by the
addition of hexadeuterobenzene (C
6D
6, spectroscopic grade) and a minor amount of hexamethyldisiloxane (HMDS, 99.5+ %),
with HMDS serving as internal standard. To give an example, about 200 mg of polymer
are dissolved in 2.0 ml of TCB, followed by addition of 0.5 ml of C
6D
6 and 2 to 3 drops of HMDS.
[0070] Following data acquisition the chemical shifts are referenced to the signal of the
internal standard HMDS, which is assigned a value of 2.03 ppm.
[0071] The isotacticity is determined by
13C-NMR analysis on the total polymer. In the spectral region of the methyl groups the
signals corresponding to the pentads mmmm, mmmr, mmrr and mrrm are assigned using
published data, for example
A. Razavi, Macromol. Symp., vol. 89, pages 345-367. Only the pentads mmmm, mmmr, mmrr and mrrm are taken into consideration due to the
weak intensity of the signals corresponding to the remaining pentads. For the signal
relating to the mmrr pentad a correction is performed for its overlap with a methyl
signal related to 2,1-insertions. The percentage of mmmm pentads is then calculated
according to

[0072] Determination of the percentage of 2,1-insertions for a metallocene propylene homopolymer:
The signals corresponding to the 2,1-insertions are identified with the aid of published
data, for example
H.N. Cheng, J. Ewen, Makromol. Chem., vol. 190 (1989), pages 1931-1940. A first area, AREA1, is defined as the average area of the signals corresponding
to 2,1-insertions. A second area, AREA2, is defined as the average area of the signals
corresponding to 1,2-insertions. The assignment of the signals relating to the 1,2-insertions
is well known to the skilled person and need not be explained further. The percentage
of 2,1-insertions is calculated according to

with the percentage in 2,1-insertions being given as the molar percentage of 2,1-inserted
propylene with respect to total propylene.
[0073] The determination of the percentage of 2,1-insertions for a metallocene random copolymer
of propylene and ethylene is determined by two contributions:
- (i) the percentage of 2,1-insertions as defined above for the propylene homopolymer,
and
- (ii) the percentage of 2,1-insertions, wherein the 2,1-inserted propylene neighbors
an ethylene,
thus the total percentage of 2,1-insertions corresponds to the sum of these two contributions.
The assignments of the signal for case (ii) can be done either by using reference
spectra or by referring to the published literature.
[0074] Melting temperatures T
melt were measured on a DSC Q2000 instrument by TA Instruments based on ISO 3146. To erase
the thermal history the samples were first heated to 200°C and kept at 200°C for a
period of 3 minutes. The reported melting temperatures T
melt were then determined with heating and cooling rates of 20°C/min.
[0075] Filament tenacity and elongation were measured on a Lenzing Vibrodyn according to
norm ISO 5079:1995 with a testing speed of 10 mm/min.
PRODUCTION OF YARN
Example
[0076] A commercially available metallocene propylene homopolymer, produced with a metallocene
polymerization catalyst comprising dimethylsilyl-bridged bis(indenyl)zirconium dichloride
as metallocene component, said metallocene polypropylene having a melt flow index
of 25 dg/min, a molecular weight distribution, defined as M
w/M
n, of 2.8, a melting temperature of 152 °C and 0.8 % of 2,1-insertions, was spun into
filaments on a Busschaert pilot line equipped with two circular dies of 112 holes,
each of a diameter of 0.5 mm. Melt temperature was kept at 250 °C. Throughput per
hole was kept constant at 0.5 g/hole/min. Take-up speed was kept at 1700 m/min. No
additional drawing step was performed. Properties were then determined on single filaments
and are reported in table 1.
Comparative example
[0077] A commercially available propylene homopolymer, produced with a Ziegler-Natta catalyst,
said propylene homopolymer having a melt flow index of 25 dg/min, a molecular weight
distribution, defined as M
w/M
n, of 4.1, a melting temperature of 162 °C and no 2,1-insertions, was spun into filaments
as described in the example above. Properties were determined on single filaments
and are reported in table 1
Table 1
| |
|
Example |
Comparative example |
| Fiber titer |
dtex |
2.9 |
3.0 |
| Tenacity at Fmax |
cN/tex |
25.5 |
19.5 |
| Elongation at break |
% |
198 |
222 |
PRODUCTION OF WOVEN FABRIC
[0078] The yarn obtained as described above may be woven on a 1 m wide ribbon loom. The
thus obtainable woven fabrics are expected to have excellent mechanical properties,
particularly tensile strength. They are also expected to be characterized by good
softness and good draping behavior.
1. Woven fabric, which comprises yarn, said yarn in turn comprising filaments, said filaments
in turn comprising a component A, said component A comprising a metallocene polypropylene.
2. Woven fabric according to claim 1, wherein the metallocene polypropylene has a molecular
weight distribution, defined as Mw/Mn, of at least 1.0 and of at most 4.0.
3. Woven fabric according to any of the preceding claims, wherein the metallocene polypropylene
has a melt flow index in the range from 5.0 dg/min to 50 dg/min as determined in accordance
with ISO 1133, condition L, at 230°C and 2.16 kg.
4. Woven fabric according to any of the preceding claims, wherein the metallocene polypropylene
is a propylene homopolymer or a random copolymer of propylene and up to 6.0 wt%, relative
to the total weight of said random copolymer, of at least one further alpha-olefin,
said at least one further alpha-olefin being different from propylene.
5. Woven fabric according to any of the preceding claims, wherein the metallocene polypropylene
has a melting temperature of at most 160°C.
6. Woven fabric according to any of the preceding claims, wherein the metallocene polypropylene
has at least 0.1 % and at most 1.5 % of 2,1 - insertions.
7. Woven fabric according to any of the preceding claims, wherein the filaments comprise
a further component B, which covers at least 50 % of the surface of said filaments,
said component B comprising a metallocene polyethylene.
8. Article comprising the woven fabric of any of claims 1 to 7.
9. Article according to claim 8, wherein the article is selected from the group consisting
of bags, sacks, nets, netting, clothing, drapes, woven belts, woven straps and upholstery.
10. Process for the production of the woven fabric of claims 1 to 6, said process comprising
the steps of
(a) providing a polymer blend comprising a metallocene polypropylene,
(b) feeding the polymer blend of step (a) to an extruder,
(c) subsequently melt-extruding the polymer blend to obtain a molten polymer stream,
(d) extruding the molten polymer stream of step (c) from a number of fine capillaries
of a spinneret, thus obtaining filaments of molten polymer,
(e) cooling the filaments obtained in step (d) to form solidified filaments,
(f) combining a number of the solidified filaments of step (e) to form a yarn, and
(g) using the yarn obtained in step (f) to form a woven fabric.
11. Process for the production of the woven fabric of claim 7, said process comprising
the steps of
(a1) providing a first polymer blend comprising a metallocene polypropylene,
(a2) providing a second polymer blend comprising a metallocene polyethylene,
(b1) providing the first polymer blend of step (a1) to a first extruder,
(b2) providing the second polymer blend of step (a2) to a second extruder,
(c1) melt-extruding the first polymer blend of step (a1) through a number of fine
capillaries of a spinneret,
(c2) melt-extruding the second polymer blend of step (a2) through a number of fine
openings surrounding said capillaries of step (c1),
(d) combining the extrudates of steps (c1) and (c2) to form single filaments of molten
polymer,
(e) cooling the filaments obtained in step (d) to form solidified filaments,
(f) combining a number of solidified filaments of step (e) to form a yarn, and
(g) using the yarn obtained in step (f) to form a woven fabric.
12. Process according to claim 10 or claim 11, wherein the metallocene polypropylene is
further defined as given in any of claims 1 to 6.
13. Process according to claim 10 or claim 11, wherein the woven fabric of step (g) is
used in to manufacture an article comprising said woven fabric.
14. Process according to claim 13, wherein the article is selected from the group consisting
of bags, sacks, nets, netting, clothing, drapes, woven belts, woven straps and upholstery.