U.S. patent application number 16/336407 was filed with the patent office on 2019-07-18 for coated polyester fabric.
The applicant listed for this patent is Dow Global Technologies LLC. Invention is credited to Burcak Conley, Miguel A. Prieto Goubert, Varun Thakur, Stefan Ultsch, Jozef J.I. Van Dun.
Application Number | 20190218708 16/336407 |
Document ID | / |
Family ID | 60084058 |
Filed Date | 2019-07-18 |
United States Patent
Application |
20190218708 |
Kind Code |
A1 |
Thakur; Varun ; et
al. |
July 18, 2019 |
Coated Polyester Fabric
Abstract
The present disclosure provides and article. The article
includes: (A) a polyester fabric; (B) a coating on a surface of the
polyester fabric, the coating comprising at least one of (i) an
ethylene/vinyl acetate/maleic anhydride terpolymer and (ii) an
ethylene/methyl acrylate/glycidyl methacrylate terpolymer.
Inventors: |
Thakur; Varun; (Horgen,
CH) ; Ultsch; Stefan; (Horgen, CH) ; Prieto
Goubert; Miguel A.; (Horgen, CH) ; Conley;
Burcak; (Zuerich, CH) ; Van Dun; Jozef J.I.;
(Horgen, CH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Global Technologies LLC |
Midland |
MI |
US |
|
|
Family ID: |
60084058 |
Appl. No.: |
16/336407 |
Filed: |
September 18, 2017 |
PCT Filed: |
September 18, 2017 |
PCT NO: |
PCT/US2017/051974 |
371 Date: |
March 25, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62400816 |
Sep 28, 2016 |
|
|
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06M 15/273 20130101;
C08K 3/013 20180101; D06B 2700/02 20130101; D06N 3/042 20130101;
B32B 27/32 20130101; D06N 3/183 20130101; B32B 27/12 20130101; D06M
15/333 20130101; B32B 27/20 20130101; C09D 131/04 20130101; D06M
2101/32 20130101; B32B 5/02 20130101; D06N 3/04 20130101; B32B 7/12
20130101; B32B 2262/0276 20130101; C09J 133/068 20130101; D06M
15/227 20130101; C09J 123/0869 20130101; D06B 1/14 20130101; C09D
123/0815 20130101; D06N 3/045 20130101; D06M 15/263 20130101; D06M
17/06 20130101; D06M 15/277 20130101 |
International
Class: |
D06M 15/273 20060101
D06M015/273; D06M 15/227 20060101 D06M015/227; D06M 17/06 20060101
D06M017/06; D06B 1/14 20060101 D06B001/14 |
Claims
1. An article comprising: (A) a polyester fabric; (B) a coating on
a surface of the polyester fabric, the coating comprising at least
one of (i) an ethylene/vinyl acetate/maleic anhydride terpolymer
and (ii) an ethylene/methyl acrylate/glycidyl methacrylate
terpolymer.
2. The article of claim 1, wherein the article is halogen-free.
3. The article of claim 1, wherein the polyester fabric is a closed
mesh polyester fabric.
4. The article of claim 1, wherein the coating comprises the
ethylene/methyl acrylate/glycidyl methacrylate terpolymer.
5. The article of claim 1, wherein the ethylene/methyl
acrylate/glycidyl methacrylate terpolymer comprises from 5 wt % to
10 wt % glycidyl methacrylate, based on the weight of the
terpolymer.
6. The article of claim 1, wherein the coating comprises
ethylene/methyl acrylate/glycidyl methacrylate terpolymer
crosslinked with a polyisocyanate.
7. The article of claim 1, wherein the coating comprises the
ethylene/vinyl acetate/maleic anhydride terpolymer.
8. The article of claim 1, wherein the ethylene/vinyl
acetate/maleic anhydride terpolymer comprises from 0.5 wt % to 3.0
wt % maleic anhydride, based on the weight of the terpolymer.
9. The article of claim 1, wherein the coating has a coat weight
from 10 g/m.sup.2 to 40 g/m.sup.2.
10. The article of claim 1 wherein the coating is an adhesive
layer, the adhesive layer adhered to the polyester fabric and
comprising at least one of (i) an ethylene/vinyl acetate/maleic
anhydride terpolymer and (ii) an ethylene/methyl acrylate/glycidyl
methacrylate terpolymer; and an outer layer, the outer layer
adhered to the adhesive layer and comprising an
ethylene/.alpha.-olefin multi-block copolymer and a filler.
11. The article of claim 10, wherein the adhesive layer comprises
the ethylene/methyl acrylate/glycidyl methacrylate terpolymer.
12. The article of claim 10, wherein the outer layer comprises from
20 wt % to 50 wt % ethylene/.alpha.-olefin multi-block copolymer
and from 50 wt % to 80 wt % filler.
13. The article of claim 10, wherein the article has a peel
strength from 12 N/cm to 50 N/cm.
Description
FIELD
[0001] The present disclosure relates to an article formed from a
coated polyester fabric, and further a polyester fabric adhered to
a polyolefin substrate.
BACKGROUND
[0002] Polyester fabric, and closed mesh polyester fabric in
particular, has numerous applications in textile architectures,
tubing, packaging films, and wire and cable applications. Polyester
fabric is conventionally coated with polyvinyl chloride (PVC) to
strengthen the fabric and provide flame retardant properties. A
need exists for a halogen-free alternative to PVC.
[0003] Polyolefins have been used as an alternative to PVC, but the
low surface energy and low polarity of polyolefins greatly limit
their applications when properties such as printing, painting or
adhesion are required. Moreover, polyolefins, alone, do not provide
flame retardant properties. A high load (40 wt % or more) of filler
is typically added to the polyolefin to provide flame retardant
properties. It is known that high load filler in polyolefin makes
polyolefin adhesion to a polyester fabric more difficult.
[0004] Conventional methods to improve the adhesion and
printability of polyolefins and polyester fabrics include surface
modification by way of physical and chemical treatments. Such
treatments include some methods such as solvent clean-up (or
wiping), surface roughening by sand paper, acid treatment and base
treatment, to some more sophisticated treatments such as plasma,
corona and flame treatments. Some of these treatments lengthen
processing time and require a more complicated processing
method.
[0005] Conventional methods also include adhesive compositions
including halogenated polyolefins, polyurethane, and/or water, but
they are typically used at a thick coat weight (greater than 40
g/m.sup.2) to improve adhesion.
[0006] A need exists for a halogen-free polyolefin-based coating
layer for polyester fabric. A need further exists for a closed mesh
polyester fabric coated with a filled polyolefin layer with strong
adhesion between the fabric and the filled polyolefin layer without
degradation to flexibility and flame retardancy.
SUMMARY
[0007] The present disclosure provides an article. The article
includes:
[0008] (A) a polyester fabric;
[0009] (B) a coating on a surface of the polyester fabric, the
coating comprising at least one of (i) an ethylene/vinyl
acetate/maleic anhydride terpolymer and (ii) an ethylene/methyl
acrylate/glycidyl methacrylate terpolymer.
[0010] The present disclosure provides another article. The article
includes:
[0011] (A) a polyester fabric;
[0012] (B) an adhesive layer, the adhesive layer adhered to the
polyester fabric and comprising at least one of (i) an
ethylene/vinyl acetate/maleic anhydride terpolymer and (ii) an
ethylene/methyl acrylate/glycidyl methacrylate terpolymer;
[0013] (C) an outer layer, the outer layer adhered to the adhesive
layer and comprising an ethylene/.alpha.-olefin multi-block
copolymer and a filler.
Definitions
[0014] Any reference to the Periodic Table of Elements is that as
published by CRC Press, Inc., 1990-1991. Reference to a group of
elements in this table is by the new notation for numbering
groups.
[0015] For purposes of United States patent practice, the contents
of any referenced patent, patent application or publication are
incorporated by reference in their entirety (or its equivalent US
version is so incorporated by reference) especially with respect to
the disclosure of definitions (to the extent not inconsistent with
any definitions specifically provided in this disclosure) and
general knowledge in the art.
[0016] The numerical ranges disclosed herein include all values
from, and including, the lower and upper value. For ranges
containing explicit values (e.g., 1 or 2; or 3 to 5; or 6; or 7),
any subrange between any two explicit values is included (e.g., 1
to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).
[0017] Unless stated to the contrary, implicit from the context, or
customary in the art, all parts and percents are based on weight
and all test methods are current as of the filing date of this
disclosure.
[0018] The term "composition" refers to a mixture of materials
which comprise the composition, as well as reaction products and
decomposition products formed from the materials of the
composition.
[0019] The terms "comprising," "including," "having" and their
derivatives, are not intended to exclude the presence of any
additional component, step or procedure, whether or not the same is
specifically disclosed. In order to avoid any doubt, all
compositions claimed through use of the term "comprising" may
include any additional additive, adjuvant, or compound, whether
polymeric or otherwise, unless stated to the contrary. In contrast,
the term "consisting essentially of" excludes from the scope of any
succeeding recitation any other component, step, or procedure,
excepting those that are not essential to operability. The term
"consisting of" excludes any component, step, or procedure not
specifically delineated or listed. The term "or," unless stated
otherwise, refers to the listed members individually as well as in
any combination. Use of the singular includes use of the plural and
vice versa.
[0020] An "ethylene-based polymer" or "ethylene polymer" is a
polymer that contains a majority amount, or greater than 50 wt %,
of polymerized ethylene based on the weight of the polymer, and,
optionally, may comprise at least one comonomer.
[0021] An "ethylene/.alpha.-olefin interpolymer" is an interpolymer
that contains a majority amount of polymerized ethylene, based on
the weight of the interpolymer, and at least one
.alpha.-olefin.
[0022] "Fabric" is a woven or non-woven (such as knitted) structure
formed from individual fibers or yarn.
[0023] "Fiber" and like terms refer to an elongated column of
entangled filaments.
[0024] "Filament" and like terms refer to a single, continuous
strand of elongated material having generally round cross-section
and a length to diameter ratio of greater than 10.
[0025] "Halogen-free" and like terms indicate that the
compositions, layers, and/or articles are without, or substantially
without, halogen content.
[0026] A "hydrocarbon" is a compound that contains only hydrogen
and carbon atoms. The hydrocarbon can be (i) branched or
unbranched, (ii) saturated or unsaturated (iii) cyclic or acyclic,
and (iv) any combination if (i)-(iii). Nonlimiting examples of
hydrocarbons include alkanes, alkenes, and alkynes.
[0027] An "interpolymer" (or "terpolymer") is a polymer prepared by
the polymerization of at least two different types of monomers. The
generic term interpolymer thus includes copolymers (employed to
refer to polymers prepared from two different types of monomers),
terpolymers (employed to refer to polymers prepared from three
different types of monomers), and polymers prepared from more than
three different types of monomers.
[0028] "Nonwoven" is a web or a fabric having a structure of
individual fibers or threads which are randomly interlaid, but no
in an identifiable manner as is the case of a knitted fabric.
[0029] An "olefin-based polymer" or "polyolefin" is a polymer that
contains a majority amount, or greater than 50 wt %, of polymerized
olefin monomer, for example, ethylene or propylene, (based on the
weight of the polymer), and optionally, may contain at least one
comonomer. Nonlimiting examples of an olefin-based polymer include
an ethylene-based polymer and a propylene-based polymer.
[0030] A "polymer" is a polymeric compound prepared by polymerizing
monomers, whether of the same or a different type. The generic term
polymer thus embraces the term "homopolymer" (employed to refer to
polymers prepared from only one type of monomer, with the
understanding that trace amounts of impurities can be incorporated
into the polymer structure), and the term "interpolymer." Trace
amounts of impurities, for example, catalyst residues, may be
incorporated into and/or within the polymer. It also embraces all
forms of copolymer, e.g., random, block, etc. The terms
"ethylene/.alpha.-olefin polymer" and "propylene/.alpha.-olefin
polymer" are indicative of copolymer as described above prepared
from polymerizing ethylene or propylene respectively and one or
more additional, polymerizable .alpha.-olefin monomer. It is noted
that although a polymer is often referred to as being "made of" one
or more specified monomers, "based on" a specified monomer or
monomer type, "containing" a specified monomer content, or the
like, in this context the term "monomer" is understood to be
referring to the polymerized remnant of the specified monomer and
not to the unpolymerized species. In general, polymers herein are
referred to has being based on "units" that are the polymerized
form of a corresponding monomer.
[0031] "Yarn" is a continuous length of twisted or otherwise
entangled filaments that can be used in the manufacture of woven or
knitted fabrics.
DETAILED DESCRIPTION
[0032] The present disclosure provides an article. The article
includes (A) a polyester fabric and (B) a coating on the surface of
the polyester fabric. The (B) coating includes at least one of (i)
an ethylene/vinyl acetate/maleic anhydride terpolymer and (ii) an
ethylene/methyl acrylate/glycidyl methacrylate terpolymer.
Optionally, the article includes (C) an outer layer. The optional
(C) outer layer includes an olefin block copolymer that is an
ethylene/.alpha.-olefin multi-block copolymer and a filler.
A. Polyester Fabric
[0033] The present article includes a polyester fabric. A
"polyester fabric" is a woven or non-woven (such as knitted)
structure formed from individual fibers or yarn, in which from
greater than 50 wt %, or 75 wt % to 90 wt %, 99 wt %, or 100 wt %
of the fibers or yarn are polyester fibers or polyester yarn. The
polyester fabric may be an open mesh fabric or a closed mesh
fabric.
[0034] In an embodiment, the polyester fabric is an open mesh
fabric. An "open mesh fabric" is a nonwoven or woven structure
formed from individual fibers or yarn, the fabric having apertures
(i.e., holes) that each have an area greater than 10,000
.mu.m.sup.2, or from greater than 10,000 .mu.m.sup.2, or 50,000
.mu.m.sup.2, or 100,000 .mu.m.sup.2 to 1 cm.sup.2, or 2 cm.sup.2.
Open mesh fabric excludes closed mesh fabric.
[0035] In an embodiment, the polyester fabric is a closed mesh
fabric. A "closed mesh fabric" is a nonwoven or woven structure
formed from individual fibers, the fabric having apertures (i.e.,
holes) that each have an area from 0 .mu.m.sup.2, or greater than 0
.mu.m.sup.2, or 1 .mu.m.sup.2, or 10 .mu.m.sup.2, or 50
.mu.m.sup.2, or 100 .mu.m.sup.2, or 500 .mu.m.sup.2 to 1,000
.mu.m.sup.2, or 5,000 .mu.m.sup.2, or less than 10,000 .mu.m.sup.2.
Closed mesh fabric excludes open-mesh fabric. In an embodiment, the
closed mesh polyester fabric is a woven close-mesh structure. A
nonlimiting example of a woven close-mesh structure is a Panama
weave, including a 2/2 weave in which the weft fiber, thread or
yarn goes over two warp fibers, threads, or yarns and then under
two warp fibers, threads, or yarns.
[0036] In an embodiment, the polyester fabric is a knitted fabric.
A "knitted fabric" is formed from intertwining yarn or fibers in a
series of connected loops either by hand, with knitting needles, or
on a machine. The polyester fabric may be formed by warp or weft
knitting, flat knitting, and circular knitting. Nonlimiting
examples of suitable warp knits include tricot, raschel powernet,
and lacing. Nonlimiting examples of suitable weft knits include
circular, flat, and seamless (which is often considered a subset of
circular knits).
[0037] A nonlimiting example of a suitable polyester is
polyethylene terephthalate (PET). In an embodiment, the article
includes a PET fabric. In a further embodiment, the article
includes a closed mesh PET fabric. In a further embodiment, the
article includes a closed mesh PET fabric having a woven close-mesh
structure (such as a Panama weave).
[0038] The polyester fabric can be subjected to any finishing
process, such as dying, pigmentation, bleaching, impregnating,
decreasing flammability, or pretreatment with an adhesion or
thermofixing agent.
[0039] In an embodiment, the polyester fabric is not subjected to
any surface modification process prior to being coated with the
present coating. Thus, the polyester fabric is not surface modified
by physical or chemical treatments. Such treatments include solvent
clean-up (or wiping); surface roughening by sand paper; acid
treatment and base treatment; and plasma, corona and flame
treatments. In an embodiment, the article includes an untreated
closed mesh PET fabric having a woven close-mesh structure (such as
a Panama weave).
[0040] In an embodiment, the polyester fabric has a thickness from
20 .mu.m, or 50 .mu.m, or 75 .mu.m, or 100 .mu.m, 150 .mu.m, or 200
.mu.m, or 250 .mu.m, or 300 .mu.m, or 350 .mu.m, or 400 .mu.m, or
450 .mu.m to 500 .mu.m, or 550 .mu.m, or 600 .mu.m, or 650 .mu.m,
or 700 .mu.m, or 750 .mu.m, or 800 .mu.m, or 900 .mu.m, or 1000
.mu.m, or 1500 .mu.m, or 2000 .mu.m, or 3000 .mu.m.
[0041] The polyester fabric may comprise two or more embodiments
disclosed herein.
B. Coating
[0042] The present article includes a coating. The coating includes
at least one of (i) an ethylene/vinyl acetate/maleic anhydride
terpolymer and (ii) an ethylene/methyl acrylate/glycidyl
methacrylate terpolymer. In an embodiment, the coating includes one
of (i) an ethylene/vinyl acetate/maleic anhydride terpolymer or
(ii) an ethylene/methyl acrylate/glycidyl methacrylate
terpolymer.
[0043] (i) Ethylene/Vinyl Acetate/Maleic Anhydride Terpolymer
[0044] In an embodiment, the coating includes an ethylene/vinyl
acetate/maleic anhydride terpolymer. An "ethylene/vinyl
acetate/maleic anhydride terpolymer" or "EVA/MAH terpolymer" is an
interpolymer that contains, in polymerized form, ethylene monomer,
vinyl acetate comonomer, and maleic anhydride comonomer.
[0045] In an embodiment, the EVA/MAH terpolymer contains from 50 wt
%, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %, or 80
wt %, or 85 wt % ethylene, based on the total weight of the EVA/MAH
terpolymer.
[0046] In an embodiment, the EVA/MAH terpolymer contains from 15 wt
%, or 20 wt %, or 25 wt %, or 26 wt % to 30 wt %, or 35 wt %, or 40
wt % vinyl acetate, based on the total weight of the EVA/MAH
terpolymer.
[0047] In an embodiment, the EVA/MAH terpolymer contains from 0.1
wt %, or 0.5 wt %, or 0.6 wt % to 0.7 wt %, or 0.8 wt %, or 0.9 wt
%, or 1.0 wt %, or 2 wt %, or 3 wt %, or 5 wt %, or 10 wt % maleic
anhydride, based on the total weight of the EVA/MAH terpolymer.
[0048] In an embodiment, the EVA/MAH terpolymer contains (a) from
50 wt %, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %,
or 80 wt %, or 85 wt % ethylene, (b) from 15 wt %, or 20 wt %, or
25 wt %, or 26 wt % to 30 wt %, or 35 wt %, or 40 wt % vinyl
acetate, and (c) from 0.1 wt %, or 0.5 wt %, or 0.6 wt % to 0.7 wt
%, or 0.8 wt %, or 0.9 wt %, or 1.0 wt %, or 2 wt %, or 3 wt %, or
5 wt %, or 10 wt % maleic anhydride, based on the total weight of
the EVA/MAH terpolymer. In a further embodiment, the EVA/MAH
terpolymer contains (a) from 69 wt %, or 69.36 wt % to 73.36 wt %,
or 74 wt % ethylene, (b) from 26 wt % to 30 wt % vinyl acetate, and
(c) 0.64 wt % maleic anhydride, based on the total weight of the
EVA/MAH terpolymer.
[0049] In an embodiment, the EVA/MAH terpolymer has a density from
0.940 g/cc, or 0.945 g/cc, or 0.950 g/cc to 0.951 g/cc, or 0.955
g/cc, or 0.960 g/cc, or 0.965 g/cc.
[0050] In an embodiment, the EVA/MAH terpolymer has a melting point
from 50.degree. C., or 55.degree. C., or 60.degree. C., or
65.degree. C. to 68.degree. C., or 70.degree. C., or 75.degree. C.,
or 80.degree. C.
[0051] In an embodiment, the EVA/MAH terpolymer has a melt index
(190.degree. C., 2.16 kg) from 130 g/10 min, or 140 g/10 min, or
150 g/10 min to 160 g/10 min, or 170 g/10 min, or 180 g/10 min, or
190 g/10 min, or 200 g/10 min, or 210 g/10 min, or 220 g/10 min, or
230 g/10 min.
[0052] In an embodiment, the EVA/MAH terpolymer has one, some, or
all of the following properties: (a) a density from 0.940 g/cc, or
0.945 g/cc, or 0.950 g/cc to 0.951 g/cc, or 0.955 g/cc, or 0.960
g/cc, or 0.965 g/cc; and/or (b) a melting point from 50.degree. C.,
or 55.degree. C., or 60.degree. C., or 65.degree. C. to 68.degree.
C., or 70.degree. C., or 75.degree. C., or 80.degree. C.; and/or
(c) a melt index (190.degree. C., 2.16 kg) from 130 g/10 min, or
140 g/10 min, or 150 g/10 min to 160 g/10 min, or 170 g/10 min, or
180 g/10 min, or 190 g/10 min, or 200 g/10 min, or 210 g/10 min, or
220 g/10 min, or 230 g/10 min.
[0053] In an embodiment, the EVA/MAH terpolymer contains (a) from
69 wt %, or 69.36 wt % to 73.36, or 74 wt % ethylene, (b) from 26
wt % to 30 wt % vinyl acetate, and (c) 0.64 wt % maleic anhydride,
based on the total weight of the EVA/MAH terpolymer, and the
EVA/MAH terpolymer has a density of 0.951 g/cc, a melting point of
68.degree. C., and a melt index (190.degree. C., 2.16 kg) from 150
g/10 min to 210 g/10 min.
[0054] In an embodiment, the EVA/MAH terpolymer is a random EVA/MAH
terpolymer. A nonlimiting example of a suitable EVA/MAH random
terpolymer is OREVAC.TM. T 9305, commercially available from
Arkema.
[0055] The EVA/MAH terpolymer may comprise two or more embodiments
disclosed herein.
[0056] (ii) Ethylene/Methyl Acrylate/Glycidyl Methacrylate
Terpolymer
[0057] In an embodiment, the coating includes an ethylene/methyl
acrylate/glycidyl methacrylate terpolymer. An "ethylene/methyl
acrylate/glycidyl methacrylate terpolymer" or "EMA/GMAterpolymer"
is an interpolymer that contains, in polymerized form, ethylene
monomer, methyl acrylate comonomer, and glycidyl methacrylate
comonomer.
[0058] In an embodiment, the EMA/GMA terpolymer contains from 50 wt
%, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %, or 80
wt %, or 85 wt % ethylene, based on the total weight of the EMA/GMA
terpolymer.
[0059] In an embodiment, the EMA/GMA terpolymer contains from 15 wt
%, or 20 wt % to 25 wt %, or 26 wt %, or 30 wt %, or 35 wt %, or 40
wt % methyl acrylate, based on the total weight of the EMA/GMA
terpolymer.
[0060] In an embodiment, the EMA/GMA terpolymer contains from 0.1
wt %, or 0.5 wt %, or 0.6 wt %, or 0.7 wt %, or 0.8 wt %, or 0.9 wt
%, or 1.0 wt %, or 2 wt %, or 5 wt % to 8 wt %, or 10 wt % glycidyl
methacrylate, based on the total weight of the EMA/GMA
terpolymer.
[0061] In an embodiment, the EMA/GMA terpolymer contains (a) from
50 wt %, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %,
or 80 wt %, or 85 wt % ethylene, (b) from 15 wt %, or 20 wt % to 25
wt %, or 26 wt %, or 30 wt %, or 35 wt %, or 40 wt % methyl
acrylate, and (c) from 0.1 wt %, or 0.5 wt %, or 0.6 wt %, or 0.7
wt %, or 0.8 wt %, or 0.9 wt %, or 1.0 wt %, or 2 wt %, or 5 wt %
to 8 wt %, or 10 wt % glycidyl methacrylate, based on the total
weight of the EMA/GMA terpolymer. In a further embodiment, the
EMA/GMA terpolymer contains (a) 68 wt % ethylene, (b) 24 wt %
methyl acrylate, and (c) 8 wt % glycidyl methacrylate, based on the
total weight of the EMA/GMA terpolymer.
[0062] In an embodiment, the EMA/GMA terpolymer has a density from
0.930 g/cc, or 0.935 g/cc, or 0.940 g/cc, or 0.945 g/cc, or 0.950
g/cc to 0.951 g/cc, or 0.955 g/cc, or 0.960 g/cc.
[0063] In an embodiment, the EMA/GMA terpolymer has a melting point
from 50.degree. C., or 55.degree. C., or 60.degree. C., or
65.degree. C. to 68.degree. C., or 70.degree. C., or 75.degree. C.,
or 80.degree. C.
[0064] In an embodiment, the EMA/GMA terpolymer has a melt index
(190.degree. C., 2.16 kg) from 1 g/10 min, or 5 g/10 min to 6 g/10
min, or 10 g/10 min, or 15 g/10 min, or 20 g/10 min, or 30 g/10
min, or 40 g/10 min, or 50 g/10 min.
[0065] In an embodiment, the EMA/GMA terpolymer has one, some, or
all of the following properties: (a) a density from 0.930 g/cc, or
0.935 g/cc, or 0.940 g/cc, or 0.945 g/cc, or 0.950 g/cc to 0.951
g/cc, or 0.955 g/cc, or 0.960 g/cc; and/or (b) a melting point from
50.degree. C., or 55.degree. C., or 60.degree. C., or 65.degree. C.
to 68.degree. C., or 70.degree. C., or 75.degree. C., or 80.degree.
C.; and/or (c) a melt index (190.degree. C., 2.16 kg) from 1 g/10
min, or 5 g/10 min to 6 g/10 min, or 10 g/10 min, or 15 g/10 min,
or 20 g/10 min, or 30 g/10 min, or 40 g/10 min, or 50 g/10 min.
[0066] In an embodiment, the EMA/GMA terpolymer contains (a) 68 wt
% ethylene, (b) 24 wt % methyl acrylate, and (c) 8 wt % glycidyl
methacrylate, based on the total weight of the EMA/GMA terpolymer,
and the EMA/GMAterpolymer has a density of 0.940 g/cc, a melting
point of 65.degree. C., and a melt index (190.degree. C., 2.16 kg)
of 6 g/10 min.
[0067] In an embodiment, the EMA/GMA terpolymer is a random EMA/GMA
terpolymer. A nonlimiting example of a suitable EMA/GMA random
terpolymer is LOTADER.TM. AX8900, commercially available from
Arkema.
[0068] The EMA/GMA terpolymer may comprise two or more embodiments
disclosed herein.
[0069] In an embodiment, the coating includes (i) an EVA/MAH
terpolymer and (ii) an EMA/GMA terpolymer.
Primer Composition
[0070] In an embodiment, (i) the ethylene/vinyl acetate/maleic
anhydride terpolymer and/or (ii) the ethylene/methyl
acrylate/glycidyl methacrylate terpolymer is applied to the (A)
polyester fabric as part of a primer composition. The primer
composition contains at least one of (i) the ethylene/vinyl
acetate/maleic anhydride terpolymer and (ii) the ethylene/methyl
acrylate/glycidyl methacrylate terpolymer; and (iii) a solvent and
(iv) optional crosslinking agent. In a further embodiment, the
primer composition contains (i) the EVA/MAH terpolymer or the
EMA/GMA terpolymer; and (ii) a solvent and (iii) optional
crosslinking agent.
[0071] Nonlimiting examples of suitable methods to apply the primer
composition to the (A) polyester fabric include drawdown, rod
coating, roller coating, brushing, dipping, pouring or spraying
techniques. In an embodiment, the primer composition is poured onto
the (A) polyester fabric and spread out by way of a coating bar or
grooved (wound) rod. In another embodiment, the primer composition
is roller coated onto the (A) polyester fabric.
[0072] (iii) Solvent
[0073] In an embodiment, a primer composition is provided. The
primer composition includes a solvent. The solvent may be a
hydrocarbon solvent, a polar solvent, and combinations thereof.
[0074] In an embodiment, the solvent is a hydrocarbon solvent. A
"hydrocarbon solvent" contains only hydrogen and carbon atoms,
including branched or unbranched, saturated or unsaturated, cyclic,
polycyclic or acyclic species, and combinations thereof. In an
embodiment, the hydrocarbon solvent is selected from aromatic
hydrocarbon solvents, aliphatic hydrocarbon solvents, and
combinations thereof. An "aromatic hydrocarbon" is a hydrocarbon
that contains one or more benzene rings. Nonlimiting examples of
aromatic hydrocarbon solvents include toluene and xylene. In an
embodiment, the hydrocarbon solvent is an aromatic hydrocarbon
solvent that is toluene. An "aliphatic hydrocarbon" is a
hydrocarbon that is an alkane, an alkene, an alkyne, or a
derivative of an alkane, an alkene or an alkyne. An aliphatic
hydrocarbon excludes aromatic hydrocarbon. Nonlimiting examples of
aliphatic hydrocarbon solvents include hexane, cyclohexane and
methylcyclohexane (MCH). In an embodiment, the hydrocarbon solvent
is an aliphatic hydrocarbon solvent containing methylcyclohexane
(MCH).
[0075] The hydrocarbon solvent may comprise two or more embodiments
disclosed herein.
[0076] In an embodiment, the solvent is a polar solvent. A "polar
solvent" is a solvent containing a polar group. A "polar group" is
any group that imparts a bond dipole moment to an otherwise
essentially nonpolar molecule. Exemplary polar groups include
alcohols, carbonyls, and carboxylic esters. Nonlimiting examples of
polar solvents include alcohols, ketones, esters, and water. In an
embodiment, the polar solvent is a ketone. Nonlimiting examples of
suitable ketones include acetone, methyl ethyl ketone and
cyclohexanone. In an embodiment, the polar solvent is an ester.
Nonlimiting examples of suitable esters include butyl acetate and
ethyl acetate. In an embodiment, the polar solvent is water.
[0077] In an embodiment, the primer composition includes a polar
solvent and a hydrocarbon solvent. In a further embodiment, the
primer composition includes a polar solvent that is an ester, such
as ethyl acetate, and a hydrocarbon solvent that is an aromatic
hydrocarbon solvent, such as toluene. In another embodiment, the
primer composition includes a polar solvent that is an ester, such
as ethyl acetate, and a hydrocarbon solvent that is an aliphatic
hydrocarbon solvent, such as methylcyclohexane (MCH).
[0078] The solvent may comprise two or more embodiments disclosed
herein.
[0079] (iv) Crosslinking Agent
[0080] In an embodiment, a primer composition is provided. The
primer composition optionally includes a crosslinking agent.
[0081] A nonlimiting example of a suitable crosslinking agent is a
polyisocyanate. A "polyisocyanate" is a molecule with at least two,
or at least three isocyanate groups in its structure. An
"isocyanate group" (or NCO) is represented by the formula:
--N.dbd.C.dbd.O.
[0082] A nonlimiting example of a suitable polyisocyanate is
tris(p-isocyanatophenyl) thiophosphate (commercially available as
DESMODUR.TM. RFE from Bayer MaterialScience).
[0083] In an embodiment, the composition excludes a crosslinking
agent.
[0084] The crosslinking agent may comprise two of more embodiments
disclosed herein.
[0085] In an embodiment, the primer composition includes:
[0086] (i) from 0 wt %, or 5 wt %, or 10 wt % to 15 wt %, or 20 wt
% of the EVA/MAH terpolymer;
[0087] (ii) from 0 wt %, or 5 wt %, or 10 wt % to 15 wt %, or 20 wt
% of the EMA/GMA terpolymer;
[0088] (iii) from 70 wt %, or 75 wt %, or 80 wt % to 85 wt %, or 88
wt %, or 90 wt %, or 95 wt % solvent; and
[0089] (iv) from 0 wt %, or 0.10 wt %, or 0.15 wt % to 0.20 wt %,
or 0.25 wt %, or 0.50 wt %, or 1.0 wt %, or 2.0 wt %, or 5.0 wt %,
or 10 wt %, or 15 wt % crosslinking agent, such as a
polyisocyanate, with the proviso that the primer composition
contains greater than 0 wt %, or from 5 wt %, or 10 wt % to 15 wt
%, or 20 wt % of at least one of the (i) EVA/MAH terpolymer and the
(ii) EMA/GMA terpolymer, based on the total weight of the primer
composition; and
the proviso that, when the EMA/GMA terpolymer is present, the
primer composition includes (iv) greater than 0 wt %, or from 0.10
wt %, or 0.15 wt % to 0.20 wt %, or 0.25 wt %, or 0.50 wt %, or 1.0
wt %, or 2.0 wt %, or 5.0 wt %, or 10 wt %, or 15 wt % crosslinking
agent; and the primer composition has one, some, or all of the
following properties: (a) a Brookfield viscosity from 50 cP, or 60
cP, or 70 cP to 75 cP, or 80 cP, or 90 cP, or 100 cP, or 125 cP, or
150 cP, or 175 cP, or 200 cP, or 210 cP, or 220 cP, or 230 cP, or
240 cP, or 250 cP; and/or (b) a pot-life from 4 hours, or greater
than 4 hours to 8 hours; and/or (c) a solids content from 5 wt %,
or 7 wt %, or 10 wt %, or 12 wt % to 15 wt %, or 20 wt %, or 25 wt
%, or 30 wt %, or 35 wt %, or 40 wt %, based on the total weight of
the primer composition. The "solids content" of the primer
composition refers to the weight of the (i) EVA/MAH terpolymer
and/or (ii) EMA/GMA terpolymer dissolved in the solvent, based on
the total weight of the primer composition.
[0090] In an embodiment, the primer composition has a pot-life from
4 hours, or greater than 4 hours to 8 hours. The "pot-life" of a
primer composition is the time between combination of a
crosslinking agent with a mixture containing a polymeric component
and a solvent, and when the combination begins to gel. A longer
pot-life is advantageous for processing because it allows for a
longer window for coating after the crosslinking agent has been
included in the primer composition, and before the primer
composition gels and becomes unsuitable for coating. Primer
compositions that do not include a crosslinking agent do not have a
pot-life.
[0091] In an embodiment, the primer composition contains the
EVA/MAH terpolymer, and the primer composition excludes a
crosslinking agent.
[0092] In an embodiment, the primer composition contains the
EMA/GMA terpolymer and a crosslinking agent, such as a
polyisocyanate.
[0093] In an embodiment, the primer composition contains an
additive. Nonlimiting examples of suitable primer composition
additives include viscosity modifiers (such as rosin esters and
cellulose), ethylene ethyl acrylate (EEA) copolymer, functionalized
EEA copolymer (such as maleic anhydride-grafted EEA copolymer),
ethylene butyl acrylate (EBA) copolymer, functionalized EVA
copolymer (such as maleic anhydride-grafted EBA copolymer), and
combinations thereof.
[0094] Advantageously, the primer composition has sufficient
penetration into the (A) polyester fabric, and into the closed mesh
polyester fabric in particular. Furthermore, the primer composition
provides high adhesion (e.g., a peel strength greater than 12 N/cm
for articles with an outer layer containing ethylene/.alpha.-olefin
multi-block copolymer and filler) for difficult-to-bond substrates
(i.e., the polyester fabric and the filled ethylene/.alpha.-olefin
multi-block copolymer outer layer).
[0095] In an embodiment, the primer composition is dried after it
is applied to the (A) polyester fabric to evaporate at least 90 wt
%, or 98 wt %, or 99 wt %, or 100 wt % of the solvent(s), based on
the weight of the solvent composition in the primer composition, to
form an adhesive layer, or a coating. In an embodiment, 100 wt % of
the solvent is evaporated, based on the weight of the total weight
of solvent in the primer composition.
[0096] The primer composition is dried to form a coating. In an
embodiment, the coating is an adhesive layer. Nonlimiting examples
of methods to dry the primer composition after it has been applied
to the (A) polyester fabric include drying the article in an oven
at a temperature equal to or greater than 90.degree. C., or equal
to or greater than 100.degree. C. for at least 0.5 minutes, at
least 1 minute, at least 2 minutes, or at least 3 minutes.
[0097] In an embodiment, the coating, and further the adhesive
layer, has a coat weight after drying of from 5 g/m.sup.2, or 10
g/m.sup.2 to 15 g/m.sup.2, or 20 g/m.sup.2, or 25 g/m.sup.2, or 30
g/m.sup.2, or 35 g/m.sup.2, or 40 g/m.sup.2.
[0098] In an embodiment, the coating, and further the adhesive
layer, includes:
[0099] (i) from 0 wt %, or 50 wt %, or 60 wt %, or 70 wt %, or 80
wt % to 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 100 wt % of
the EVA/MAH terpolymer;
[0100] (ii) from 0 wt %, or 50 wt %, or 60 wt %, or 70 wt %, or 80
wt % to 90 wt %, or 95 wt %, or 98 wt %, or 99 wt %, or 100 wt % of
the EMA/GMA terpolymer;
[0101] (iii) from 0 wt % to 1 wt %, or 2 wt %, or 5 wt %, or 10 wt
% solvent; and
[0102] (iv) from 0 wt %, or 0.10 wt %, or 0.15 wt % to 0.20 wt %,
or 0.25 wt %, or 0.50 wt %, or 1.0 wt %, or 2.0 wt %, or 5.0 wt %,
or 10 wt %, or 15 wt % crosslinking agent,
with the proviso that the coating contains greater than 0 wt %, or
from 50 wt %, or 60 wt %, or 70 wt %, or 80 wt % to 90 wt %, or 95
wt %, or 98 wt %, or 99 wt %, or 100 wt % of at least one of the
(i) EVA/MAH terpolymer and the (ii) EMA/GMA terpolymer, based on
the total weight of the coating; and the proviso that, when the
EMA/GMAterpolymer is present, the coating includes (iv) greater
than 0 wt %, or from 0.10 wt %, or 0.15 wt % to 0.20 wt %, or 0.25
wt %, or 0.50 wt %, or 1.0 wt %, or 2.0 wt %, or 5.0 wt %, or 10 wt
%, or 15 wt % crosslinking agent.
[0103] In an embodiment, the article includes (A) a polyester
fabric; and (B) a coating on a surface of the polyester fabric, the
coating containing the EVA/MAH terpolymer, and the coating
excluding a crosslinking agent, and the coating excluding the
EMA/GMAterpolymer, and the article is halogen-free. In a further
embodiment, the coating includes from 50 wt %, or 60 wt %, or 70 wt
% to 80 wt %, or 90 wt %, or 95 wt %, or 99 wt %, or 100 wt %
EVA/MAH, based on the total weight of the coating (dried).
[0104] In an embodiment, the article includes (A) a polyester
fabric; and (B) a coating on a surface of the polyester fabric, the
coating containing the EMA/GMAterpolymer crosslinked with a
crosslinking agent such as a polyisocyanate, and the coating
excludes the EVA/MAH terpolymer. The polyester fabric can be any
polyester fabric disclosed herein, such as a closed mesh PET
fabric. In a further embodiment, the coating includes from 50 wt %,
or 60 wt %, or 70 wt % to 80 wt %, or 85 wt %, or 90 wt %, or 95 wt
%, or 99 wt %, or less than 100 wt % EMA/GMA and from greater than
0 wt %, or from 0.10 wt %, or 0.15 wt % to 0.20 wt %, or 0.25 wt %,
or 0.50 wt %, or 1.0 wt %, or 2.0 wt %, or 5.0 wt %, or 10 wt %, or
15 wt % crosslinking agent based on the total weight of the coating
(dried).
[0105] The coating may comprise two or more embodiments disclosed
herein.
C. Outer Layer
[0106] In an embodiment, the present article includes an optional
outer layer. When the outer layer is present it is adhered to the
coating, or further is adhered to the adhesive layer. The outer
layer includes (i) an olefin block copolymer that is an
ethylene/.alpha.-olefin multi-block copolymer and (ii) a filler,
and (iii) optional additive.
[0107] (i) Olefin Block Copolymer
[0108] The outer layer includes an olefin block copolymer. The term
"olefin block copolymer" or "OBC" refers to an
ethylene/.alpha.-olefin multi-block copolymer and includes ethylene
and one or more copolymerizable .alpha.-olefin comonomer in
polymerized form, characterized by multiple blocks or segments of
two or more polymerized monomer units differing in chemical or
physical properties. The term "ethylene/.alpha.-olefin multi-block
copolymer" includes block copolymer with two blocks (di-block) and
more than two blocks (multi-block). The terms "interpolymer" and
"copolymer" are used interchangeably herein. When referring to
amounts of "ethylene" or "comonomer" in the copolymer, it is
understood that this refers to polymerized units thereof. In some
embodiments, the ethylene/.alpha.-olefin multi-block copolymer can
be represented by the following formula:
(AB).sub.n
where n is at least 1, preferably an integer greater than 1, such
as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or
higher, "A" represents a hard block or segment, and "B" represents
a soft block or segment. Preferably, As and Bs are linked, or
covalently bonded, in a substantially linear fashion, or in a
linear manner, as opposed to a substantially branched or
substantially star-shaped fashion. In other embodiments, A blocks
and B blocks are randomly distributed along the polymer chain. In
other words, the block copolymers usually do not have a structure
as follows:
AAA-AA-BBB-BB
[0109] In still other embodiments, the block copolymers do not
usually have a third type of block, which comprises different
comonomer(s). In yet other embodiments, each of block A and block B
has monomers or comonomers substantially randomly distributed
within the block. In other words, neither block A nor block B
comprises two or more sub-segments (or sub-blocks) of distinct
composition, such as a tip segment, which has a substantially
different composition than the rest of the block.
[0110] Preferably, ethylene comprises the majority mole fraction of
the whole block copolymer, i.e., ethylene comprises at least 50
mole percent of the whole polymer. More preferably ethylene
comprises at least 60 mole percent, at least 70 mole percent, or at
least 80 mole percent, with the substantial remainder of the whole
polymer comprising at least one other comonomer that is preferably
an .alpha.-olefin having 3 or more carbon atoms. In some
embodiments, the ethylene/.alpha.-olefin multi-block copolymer may
comprise 50 mol % to 90 mol % ethylene, or 60 mol % to 85 mol %
ethylene, or 65 mol % to 80 mol % ethylene. For many
ethylene/octene multi-block copolymers, the composition comprises
an ethylene content greater than 80 mole percent of the whole
polymer and an octene content of from 10 to 15 mole percent, or
from 15 to 20 mole percent of the whole polymer.
[0111] The ethylene/.alpha.-olefin multi-block copolymer includes
various amounts of "hard" segments and "soft" segments. "Hard"
segments are blocks of polymerized units in which ethylene is
present in an amount greater than 90 weight percent, or 95 weight
percent, or greater than 95 weight percent, or greater than 98
weight percent based on the weight of the polymer, up to 100 weight
percent. In other words, the comonomer content (content of monomers
other than ethylene) in the hard segments is less than 10 weight
percent, or 5 weight percent, or less than 5 weight percent, or
less than 2 weight percent based on the weight of the polymer, and
can be as low as zero. In some embodiments, the hard segments
include all, or substantially all, units derived from ethylene.
"Soft" segments are blocks of polymerized units in which the
comonomer content (content of monomers other than ethylene) is
greater than 5 weight percent, or greater than 8 weight percent,
greater than 10 weight percent, or greater than 15 weight percent
based on the weight of the polymer. In some embodiments, the
comonomer content in the soft segments can be greater than 20
weight percent, greater than 25 weight percent, greater than 30
weight percent, greater than 35 weight percent, greater than 40
weight percent, greater than 45 weight percent, greater than 50
weight percent, or greater than 60 weight percent and can be up to
100 weight percent.
[0112] The soft segments can be present in an
ethylene/.alpha.-olefin multi-block copolymer from 1 wt % to 99 wt
% of the total weight of the ethylene/.alpha.-olefin multi-block
copolymer, or from 5 wt % to 95 wt %, from 10 wt % to 90 wt %, from
15 wt % to 85 wt %, from 20 wt % to 80 wt %, from 25 wt % to 75 wt
%, from 30 wt % to 70 wt %, from 35 wt % to 65 wt %, from 40 wt %
to 60 wt %, or from 45 wt % to 55 wt % of the total weight of the
ethylene/.alpha.-olefin multi-block copolymer. Conversely, the hard
segments can be present in similar ranges. The soft segment weight
percentage and the hard segment weight percentage can be calculated
based on data obtained from DSC or NMR. Such methods and
calculations are disclosed in, for example, U.S. Pat. No.
7,608,668, entitled "Ethylene/.alpha.-Olefin Block Inter-Polymers,"
filed on Mar. 15, 2006, in the name of Colin L. P. Shan, Lonnie
Hazlitt, et. al. and assigned to Dow Global Technologies Inc., the
disclosure of which is incorporated by reference herein in its
entirety. In particular, hard and soft segment weight percentages
and comonomer content may be determined as described in column 57
to column 63 of U.S. Pat. No. 7,608,668.
[0113] The ethylene/.alpha.-olefin multi-block copolymer is a
polymer comprising two or more chemically distinct regions or
segments (referred to as "blocks") preferably joined (or covalently
bonded) in a linear manner, that is, a polymer comprising
chemically differentiated units which are joined end-to-end with
respect to polymerized ethylenic functionality, rather than in
pendent or grafted fashion. In an embodiment, the blocks differ in
the amount or type of incorporated comonomer, density, amount of
crystallinity, crystallite size attributable to a polymer of such
composition, type or degree of tacticity (isotactic or
syndiotactic), regio-regularity or regio-irregularity, amount of
branching (including long chain branching or hyper-branching),
homogeneity or any other chemical or physical property. Compared to
block interpolymers of the prior art, including interpolymers
produced by sequential monomer addition, fluxional catalysts, or
anionic polymerization techniques, the present
ethylene/.alpha.-olefin multi-block copolymer is characterized by
unique distributions of both polymer polydispersity (PDI or Mw/Mn
or MWD), polydisperse block length distribution, and/or
polydisperse block number distribution, due, in an embodiment, to
the effect of the shuttling agent(s) in combination with multiple
catalysts used in their preparation.
[0114] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer is produced in a continuous process and possesses a
polydispersity index (Mw/Mn) from 1.7 to 3.5, or from 1.8 to 3, or
from 1.8 to 2.5, or from 1.8 to 2.2. When produced in a batch or
semi-batch process, the ethylene/.alpha.-olefin multi-block
copolymer possesses Mw/Mn from 1.0 to 3.5, or from 1.3 to 3, or
from 1.4 to 2.5, or from 1.4 to 2.
[0115] In addition, the ethylene/.alpha.-olefin multi-block
copolymer possesses a PDI (or Mw/Mn) fitting a Schultz-Flory
distribution rather than a Poisson distribution. The present
ethylene/.alpha.-olefin multi-block copolymer has both a
polydisperse block distribution as well as a polydisperse
distribution of block sizes. This results in the formation of
polymer products having improved and distinguishable physical
properties. The theoretical benefits of a polydisperse block
distribution have been previously modeled and discussed in
Potemkin, Physical Review E (1998) 57 (6), pp. 6902-6912, and
Dobrynin, J. Chem. Phvs. (1997) 107 (21), pp 9234-9238.
[0116] In an embodiment, the present ethylene/.alpha.-olefin
multi-block copolymer possesses a most probable distribution of
block lengths.
[0117] In a further embodiment, the ethylene/.alpha.-olefin
multi-block copolymer of the present disclosure, especially those
made in a continuous, solution polymerization reactor, possess a
most probable distribution of block lengths. In one embodiment of
this disclosure, the ethylene multi-block interpolymers are defined
as having:
[0118] (A) Mw/Mn from about 1.7 to about 3.5, at least one melting
point, Tm, in degrees Celsius, and a density, d, in grams/cubic
centimeter, where in the numerical values of Tm and d correspond to
the relationship:
Tm>-2002.9+4538.5(d)-2422.2(d).sup.2, and/or
[0119] (B) Mw/Mn from about 1.7 to about 3.5, and is characterized
by a heat of fusion, .DELTA.H in J/g, and a delta quantity,
.DELTA.T, in degrees Celsius defined as the temperature difference
between the tallest DSC peak and the tallest Crystallization
Analysis Fractionation ("CRYSTAF") peak, wherein the numerical
values of .DELTA.T and .DELTA.H have the following
relationships:
.DELTA.T>-0.1299 .DELTA.H+62.81 for .DELTA.H greater than zero
and up to 130 J/g
.DELTA.T.gtoreq.48.degree. C. for .DELTA.H greater than 130 J/g
wherein the CRYSTAF peak is determined using at least 5 percent of
the cumulative polymer, and if less than 5 percent of the polymer
has an identifiable CRYSTAF peak, then the CRYSTAF temperature is
30.degree. C.; and/or
[0120] (C) elastic recovery, Re, in percent at 300 percent strain
and 1 cycle measured with a compression-molded film of the
ethylene/.alpha.-olefin interpolymer, and has a density, d, in
grams/cubic centimeter, wherein the numerical values of Re and d
satisfy the following relationship when ethylene/.alpha.-olefin
interpolymer is substantially free of crosslinked phase:
Re>1481-1629(d); and/or
[0121] (D) has a molecular fraction which elutes between 40.degree.
C. and 130.degree. C. when fractionated using TREF, characterized
in that the fraction has a molar comonomer content of at least 5
percent higher than that of a comparable random ethylene
interpolymer fraction eluting between the same temperatures,
wherein said comparable random ethylene interpolymer has the same
comonomer(s) and has a melt index, density and molar comonomer
content (based on the whole polymer) within 10 percent of that of
the ethylene/.alpha.-olefin interpolymer; and/or
[0122] (E) has a storage modulus at 25.degree. C., G'(25.degree.
C.), and a storage modulus at 100.degree. C., G'(100.degree. C.),
wherein the ratio of G'(25.degree. C.) to G'(100.degree. C.) is in
the range of 1:1 to 9:1.
[0123] The ethylene/.alpha.-olefin multi-block copolymer may also
have:
[0124] (F) a molecular fraction which elutes between 40.degree. C.
and 130.degree. C. when fractionated using TREF, characterized in
that the fraction has a block index of at least 0.5 and up to 1 and
a molecular weight distribution, Mw/Mn, greater than 1.3;
and/or
[0125] (G) average block index greater than zero and up to 1.0 and
a molecular weight distribution, Mw/Mn greater than 1.3.
[0126] It is understood that the ethylene/.alpha.-olefin
multi-block copolymer may have one, some, all, or any combination
of properties (A)-(G). Block Index can be determined as described
in detail in U.S. Pat. No. 7,608,668 herein incorporated by
reference for that purpose. Analytical methods for determining
properties (A) through (G) are disclosed in, for example, U.S. Pat.
No. 7,608,668, col. 31 line 26 through col. 35 line 44, which is
herein incorporated by reference for that purpose.
[0127] Suitable monomers for use in preparing the present
ethylene/.alpha.-olefin multi-block copolymer include ethylene and
one or more addition polymerizable monomers other than ethylene.
Examples of suitable comonomers include straight-chain or branched
.alpha.-olefins of 3 to 30, or 3 to 20, or 4 to 8 carbon atoms,
such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene,
1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene,
1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and
1-eicosene; cyclo-olefins of 3 to 30, or 3 to 20, carbon atoms,
such as cyclopentene, cycloheptene, norbornene,
5-methyl-2-norbornene, tetracyclododecene, and
2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene;
di- and polyolefins, such as butadiene, isoprene,
4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene,
1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene,
1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene,
ethylidenenorbornene, vinyl norbornene, dicyclopentadiene,
7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and
5,9-dimethyl-1,4,8-decatriene; and 3-phenylpropene,
4-phenylpropene, 1,2-difluoroethylene, tetrafluoroethylene, and
3,3,3-trifluoro-1-propene.
[0128] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer is void of, or otherwise excludes, styrene (i.e., is
styrene-free), and/or vinyl aromatic monomer, and/or conjugated
diene.
[0129] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer consists of ethylene and a comonomer that is a
C.sub.4-C.sub.8 .alpha.-olefin. The C.sub.4-C.sub.8 .alpha.-olefin
is selected from butene, hexene, and octene.
[0130] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer has hard segments and soft segments, is styrene-free,
consists of only (i) ethylene and (ii) a C.sub.4-C.sub.8
.alpha.-olefin, and is defined as having a Mw/Mn from 1.7 to 3.5,
at least one melting point, Tm, in degrees Celsius, and a density,
d, in grams/cubic centimeter, wherein the numerical values of Tm
and d correspond to the relationship:
Tm>-2002.9+4538.5(d)-2422.2(d).sup.2,
where the density, d, is from 0.850 g/cc, or 0.860 g/cc, or 0.870
g/cc, or 0.875 g/cc to 0.880 g/cc, or 0.890 g/cc; and the melting
point, Tm, is from 110.degree. C., or 115.degree. C., or
120.degree. C. to 125.degree. C., or 130.degree. C., or 135.degree.
C.
[0131] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer is an ethylene/octene multi-block copolymer (consisting
only of ethylene and octene comonomer) and has one, some, any
combination of, or all of the following properties (1)-(12): (1) a
Mw/Mn from 1.7, or 1.8 to 2.2, or 2.5, or 3.5; and/or (2) a density
from 0.850 g/cc, or 0.860 g/cc, or 0.870 g/cc, or 0.875 g/cc to
0.880 g/cc, or 0.890 g/cc; and/or (3) a melting point, Tm, from
110.degree. C., or 115.degree. C., or 120.degree. C. to 125.degree.
C., or 130.degree. C., or 135.degree. C.; and/or (4) a Shore A
value of 40, or 50, or 55, or 60, or 76, or 70 to 75, or 77, or 80,
or 85; and/or (5) a melt index (MI) from 0.1 g/10 min, or 0.5 g/10
min to 1.0 g/10 min, or 2.0 g/10 min, or 5 g/10 min, or 10 g/10
min, or 15 g/10 min, or 20 g/10 min, or 30 g/10 min; and/or (6) a
tensile strength at break from 7 PMa, or 10 MPa, or 13 MPa to 14
MPa, or 15 MPa, or 20 MPa, or 25 MPa, or 30 MPa; and/or (7) an
elongation at break from 500%, or 600%, or 700%, or 750% to 800%,
or 900%, or 1000%; and/or (8) 50-85 wt % soft segment and 40-15 wt
% hard segment; and/or (9) from 10 mol %, or 13 mol %, or 14 mol %,
or 15 mol % to 16 mol %, or 17 mol %, or 18 mol %, or 19 mol %, or
20 mol % C.sub.4-C.sub.12 .alpha.-olefin in the soft segment;
and/or (10) from 0.5 mol %, or 1.0 mol %, or 2.0 mol %, or 3.0 mol
% to 4.0 mol %, or 5 mol %, or 6 mol %, or 7 mol %, or 9 mol %
octene in the hard segment; and/or (11) an elastic recovery (Re)
from 50%, or 60% to 70%, or 80%, or 90%, at 300% 300% min.sup.-1
deformation rate at 21.degree. C. as measured in accordance with
ASTM D 1708; and/or (12) a polydisperse distribution of blocks and
a polydisperse distribution of block sizes.
[0132] In an embodiment, the ethylene/.alpha.-olefin multi-block
copolymer is an ethylene/octene multi-block copolymer. In a further
embodiment, the ethylene/.alpha.-olefin multi-block copolymer is an
ethylene/octene block copolymer having one, some, or all of the
following properties: a melt index (190.degree. C./2.16 kg) of 0.50
g/10 min, a melting point of 122.degree. C., a density of 0.879
g/cc, a Shore A value of 77, a tensile strength at break equal to
or greater than 13.2 MPa, and/or an elongation at break equal to or
greater than 750%.
[0133] In an embodiment, the ethylene/octene multi-block copolymer
is sold under the tradename INFUSE.TM., available from The Dow
Chemical Company, Midland, Mich., USA. In a further embodiment, the
ethylene/octene multi-block copolymer is INFUSE.TM. 9010.
[0134] The ethylene/.alpha.-olefin multi-block copolymers can be
produced via a chain shuttling process such as described in U.S.
Pat. No. 7,858,706, which is herein incorporated by reference. In
particular, suitable chain shuttling agents and related information
are listed in col. 16 line 39 through col. 19 line 44. Suitable
catalysts are described in col. 19 line 45 through col. 46 line 19
and suitable co-catalysts in col. 46 line 20 through col. 51 line
28. The process is described throughout the document, but
particularly in col. 51 line 29 through col. 54 line 56. The
process is also described, for example, in the following: U.S. Pat.
Nos. 7,608,668; 7,893,166; and 7,947,793.
[0135] The outer layer may comprise more than one
ethylene/.alpha.-olefin multi-block copolymer.
[0136] In an embodiment, the outer layer contains from 20 wt %, or
25 wt %, or 30 wt % to 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %
ethylene/.alpha.-olefin multi-block copolymer, based on the total
weight of the outer layer.
[0137] The ethylene/.alpha.-olefin multi-block copolymer may
comprise two or more embodiments disclosed herein.
[0138] (ii) Filler
[0139] The outer layer includes a filler. Nonlimiting examples of
suitable fillers include carbon black; calcium carbonate
(CaCO.sub.3); clay; nanoclay; talc; silica; coal fly ash; any
natural or synthetic, inorganic or organic compounds such as
zeolite, magnesium hydroxide (MDH), aluminum trihydroxide (ATH),
titanium dioxide (TiO.sub.2), and aluminum hydroxide; layered
double hydroxides, ammonium polyphosphates; phosphinates; monomeric
phosphonates; oligomeric phosphonates; polyphosphonates; and
combinations thereof. In an embodiment, the filler is magnesium
hydroxide (MDH), such as Magnifin.TM. H-5 MV, available from
Albemarle.
[0140] The outer layer may include more than one filler. In an
embodiment, the outer layer includes magnesium hydroxide (MDH) and
titanium dioxide (TiO.sub.2).
[0141] In an embodiment, the outer layer contains from 40 wt %, or
45 wt %, or 50 wt %, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %,
or 75 wt %, or 80 wt % filler, based on the total weight of the
outer layer.
[0142] In an embodiment, the outer layer contains from 20 wt %, or
25 wt %, or 30 wt % to 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %
ethylene/.alpha.-olefin multi-block copolymer; and a reciprocal
amount of filler or from 50 wt %, or 55 wt %, or 60 wt %, or 65 wt
% to 70 wt %, or 75 wt %, or 80 wt % filler.
[0143] The filler may comprise two or more embodiments disclosed
herein.
[0144] (iii) Additive
[0145] The present outer layer may include one or more additives.
Nonlimiting examples of suitable additives include antioxidants,
colorants, ultra violet (UV) absorbers or stabilizers,
anti-blocking agents, flame retardants, coupling agents,
compatibilizers, plasticizers, processing aids, and combinations
thereof.
[0146] In an embodiment, the outer layer includes an antioxidant.
Nonlimiting examples of suitable antioxidants include phenolic
antioxidants, thio-based antioxidants, phosphate-based
antioxidants, and hydrazine-based metal deactivators. Suitable
phenolic antioxidants include high molecular weight hindered
phenols, methyl-substituted phenol, phenols having substituents
with primary or secondary carbonyls, and multifunctional phenols
such as sulfur and phosphorous-containing phenol. In an embodiment,
the antioxidant is pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate),
commercially available as Irganox.RTM. 1010 from BASF. In an
embodiment, the antioxidant is
tris(2,4-ditert-butylphenyl)phosphite, commercially available as
IRGAFOS.TM. 168 from Ciba, Inc. In a further embodiment, the outer
layer includes a blend of Irganox.RTM. 1010 and IRGAFOS.TM. 168
(commercially available as Irganox.TM. B 225 from BASF). In an
embodiment, the outer layer contains from 0 wt %, or 0.001 wt %, or
0.01 wt %, or 0.02 wt %, or 0.05 wt %, or 0.1 wt %, or 0.2 wt %, or
0.3 wt %, or 0.4 wt % to 0.5 wt %, or 0.6 wt %, or 0.7 wt %, or 0.8
wt %, or 1.0 wt %, or 2.0 wt %, or 2.5 wt %, or 3.0 wt %
antioxidant, based on total weight of the outer layer.
[0147] In an embodiment, the outer layer includes an ultra violet
(UV) absorber or stabilizer. A nonlimiting example of a suitable UV
stabilizer is a hindered amine light stabilizer (HALS). A
nonlimiting examples of a suitable HALS is Chimassorb.TM. 2020
(commercially available from BASF). In an embodiment, the outer
layer contains from 0 wt %, or 0.001 wt %, or 0.002 wt %, or 0.005
wt %, or 0.006 wt % to 0.007 wt %, or 0.008 wt %, or 0.009 wt %, or
0.01 wt %, or 0.2 wt %, or 0.3 wt %, or 0.4 wt %, or 0.5 wt %, 1.0
wt %, or 2.0 wt %, or 2.5 wt %, or 3.0 wt % UV absorber or
stabilizer, based on total weight of the outer layer.
[0148] In an embodiment, the outer layer contains from 20 wt %, or
25 wt %, or 30 wt % to 35 wt %, or 40 wt %, or 45 wt %, or 50 wt %
ethylene/.alpha.-olefin multi-block copolymer; from 40 wt %, or 45
wt %, or 50 wt %, or 55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or
75 wt %, or 80 wt % filler; and from 0 wt %, or greater than 0 wt
%, or 0.001 wt %, or 0.002 wt %, or 0.005 wt %, or 0.006 wt % to
0.007 wt %, or 0.008 wt %, or 0.009 wt %, or 0.01 wt %, or 0.2 wt
%, or 0.3 wt %, or 0.4 wt %, or 0.5 wt %, 1.0 wt %, or 2.0 wt %, or
2.5 wt %, or 3.0 wt %, or 4.0 wt %, or 5.0 wt % to 6.0 wt %, or 7.0
wt %, or 8.0 wt %, or 9.0 wt %, or 10.0 wt % additive, based on the
total weight of the outer layer.
[0149] Not wishing to be bound by any particular theory, Applicant
believes the high filler load (from 40 wt %, or 60 wt % to 65 wt %,
or 75 wt %, or 80 wt % filler) provides flame retardant properties
to the outer layer containing ethylene/.alpha.-olefin multi-block
copolymer.
[0150] The outer layer may comprise two or more embodiments
disclosed herein.
[0151] It is understood that the sum of the components in each of
the compositions and layers disclosed herein, including the
foregoing compositions, yields 100 weight percent (wt %).
D. Article
[0152] The present disclosure provides an article. The article
includes (A) a polyester fabric and (B) a coating on the surface of
the polyester fabric. The coating includes at least one of (i) an
EVA/MAH terpolymer and (ii) an EMA/GMA terpolymer. Optionally, the
article includes (C) an outer layer and the article has a structure
A/B/C. The optional (C) outer layer includes an olefin block
copolymer that is an ethylene/.alpha.-olefin multi-block copolymer
and a filler.
[0153] The present disclosure provides another article. The article
includes (A) a polyester fabric and (B) a coating that is an
adhesive layer, the adhesive layer adhered to the polyester fabric
and including at least one of (i) an EVA/MAH terpolymer and (ii) an
EMA/GMA terpolymer; and (C) an outer layer, the outer layer adhered
to the adhesive layer and including an ethylene/.alpha.-olefin
multi-block copolymer and a filler.
[0154] In an embodiment, the adhesive layer contains either (i) the
EVA/MAH terpolymer or (ii) the EMA/GMA terpolymer.
[0155] The polyester fabric, coating, adhesive layer, and outer
layer may be any respective polyester fabric, coating, and outer
layer disclosed herein. In an embodiment, the polyester fabric is a
closed mesh polyester fabric. In a further embodiment, the
polyester fabric is a closed mesh PET fabric.
[0156] Nonlimiting examples of suitable articles include coated
fabrics; textile architectures such as banners and tents;
reinforced tubing; multi-layer packaging films; and wire and cable
applications.
[0157] In an embodiment, the article includes (A) a polyester
fabric and (B) a coating that is an adhesive layer, the adhesive
layer adhered to the polyester fabric and including at least one of
(i) an EVA/MAH terpolymer and (ii) an EMA/GMA terpolymer; and (C)
an outer layer, the outer layer adhered to the adhesive layer and
including an ethylene/.alpha.-olefin multi-block copolymer and a
filler; and the article has a structure A/B/C. In an embodiment,
the article has a peel strength from 12 N/cm, or greater than 12
N/cm, or 16 N/cm to 20 N/cm, or 25 N/cm, or 30 N/cm, or 35 N/cm, or
40 N/cm, or 45 N/cm, or 50 N/cm.
[0158] In an embodiment, the article is halogen-free. A
halogen-free article excludes polyvinyl chloride (PVC).
[0159] In an embodiment, the outer layer is extruded onto the
coating or adhesive layer adhered to the polyester fabric. In an
embodiment, the outer layer is extruded onto the coating or
adhesive layer adhered to the polyester fabric at an extrusion
temperature from 250.degree. C., or 260.degree. C., or 270.degree.
C. to 280.degree. C., or 290.degree. C., or 300.degree. C. In an
embodiment, after the outer layer is extruded onto the coating or
adhesive layer adhered to the polyester fabric, the article is
passed through a series of calendar rolls.
[0160] In an embodiment, the article with the A/B/C layer structure
has a thickness from 0.5 mm, or 1.0 mm to 1.5 mm, or 2.0 mm, or 2.5
mm, or 3.0 mm, or 4.0 mm, or 5.0 mm, or 10 mm, or 20 mm.
[0161] Without wishing to be bound by any particular theory,
Applicant believes a coating containing at least one of (i) an
EVA/MAH terpolymer and (ii) an EMA/GMA terpolymer is compatible
with both the ethylene/.alpha.-olefin multi-block copolymer and
filler layer and the polyester fabric, resulting in improved
adhesion between the (A) polyester fabric and (C) outer layer
containing the ethylene/.alpha.-olefin multi-block copolymer and
filler. In an embodiment, the article has a peel strength from 12
N/cm, or greater than 12 N/cm, or 16 N/cm to 20 N/cm, or 25 N/cm,
or 30 N/cm, or 35 N/cm, or 40 N/cm, or 45 N/cm, or 50 N/cm.
Further, the coating containing at least one of (i) an EVA/MAH
terpolymer and (ii) an EMA/GMA terpolymer may advantageously be
present at a low coat weight (from 5 g/m.sup.2, or 10 g/m.sup.2 to
15 g/m.sup.2, or 20 g/m.sup.2, or 40 g/m.sup.2), which results in
lower production costs.
[0162] In an embodiment, the article includes:
[0163] (A) a polyester fabric, such as a closed mesh polyester
fabric or further a closed mesh PET fabric;
[0164] (B) a coating that is an adhesive layer, the adhesive layer
adhered to the polyester fabric and including an EVA/MAH
terpolymer; and
[0165] (C) an outer layer, the outer layer adhered to the adhesive
layer and including from 20 wt %, or 25 wt %, or 30 wt % to 35 wt
%, or 40 wt %, or 45 wt %, or 50 wt % ethylene/.alpha.-olefin
multi-block copolymer and from 40 wt %, or 45 wt %, or 50 wt %, or
55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %, or 80 wt %
filler, and optional additive; and
[0166] the coating and/or the article are halogen-free; and
[0167] the article has a structure A/B/C; and the article has one,
some, any combination of, or all of the following properties
(1)-(3): (1) a peel strength from 12 N/cm, or greater than 12 N/cm,
or 16 N/cm to 20 N/cm, or 25 N/cm, or 30 N/cm, or 35 N/cm, or 40
N/cm, or 45 N/cm, or 50 N/cm; and/or (2) the coating has a coat
weight from 5 g/m.sup.2, or 10 g/m.sup.2 to 15 g/m.sup.2, or 20
g/m.sup.2, or 25 g/m.sup.2, or 30 g/m.sup.2, or 35 g/m.sup.2, or 40
g/m.sup.2; and/or (3) the article has a thickness from 0.5 mm, or
1.0 mm to 1.5 mm, or 2.0 mm, or 2.5 mm, or 3.0 mm, or 4.0 mm, or
5.0 mm, or 10 mm, or 20 mm.
[0168] In an embodiment, the article includes:
[0169] (A) a polyester fabric, such as a closed mesh polyester
fabric or further a closed mesh PET fabric;
[0170] (B) a coating that is an adhesive layer, the adhesive layer
adhered to the polyester fabric and including an EMA/GMA terpolymer
crosslinked with a crosslinking agent such as a polyisocyanate;
and
[0171] (C) an outer layer, the outer layer adhered to the adhesive
layer and including from 20 wt %, or 25 wt %, or 30 wt % to 35 wt
%, or 40 wt %, or 45 wt %, or 50 wt % ethylene/.alpha.-olefin
multi-block copolymer and from 40 wt %, or 45 wt %, or 50 wt %, or
55 wt %, or 60 wt % to 65 wt %, or 70 wt %, or 75 wt %, or 80 wt %
filler, and optional additive; and
[0172] the coating and/or the article are halogen-free; and
[0173] the article has a structure A/B/C; and the article has one,
some, any combination of, or all of the following properties
(1)-(3): (1) a peel strength from 12 N/cm, or greater than 12 N/cm,
or 16 N/cm to 20 N/cm, or 25 N/cm, or 30 N/cm, or 35 N/cm, or 40
N/cm, or 45 N/cm, or 50 N/cm; and/or (2) the coating has a coat
weight from 5 g/m.sup.2, or 10 g/m.sup.2 to 15 g/m.sup.2, or 20
g/m.sup.2, or 25 g/m.sup.2, or 30 g/m.sup.2, or 35 g/m.sup.2, or 40
g/m.sup.2; and/or (3) the article has a thickness from 0.5 mm, or
1.0 mm to 1.5 mm, or 2.0 mm, or 2.5 mm, or 3.0 mm, or 4.0 mm, or
5.0 mm, or 10 mm, or 20 mm.
[0174] The article may comprise two or more embodiments disclosed
herein.
Test Methods
[0175] Density is measured in accordance with ASTM D792, Method B.
The result is recorded in grams (g) per cubic centimeter (g/cc or
g/cm.sup.3).
[0176] Melt index (MI) (I.sub.2) is measured according to ASTM
D1238, Condition 190.degree. C./2.16 kilogram (kg) weight, and is
reported in grams eluted per 10 minutes (g/10 min).
[0177] Melt Flow (MF) for the styrenic block copolymer is measured
in accordance with ASTM D1238, Condition 230.degree. C./5.0
kilogram (kg) weight and is reported in g/10 min.
[0178] Brookfield viscosity is measured using a Brookfield DV-1
Prime Viscometer. The spindle selection depends on the viscosity of
the sample. For samples that are more viscous, or gelled, spindle
TF96 is used. For samples that are less viscous, either spindle
LV62 or LV63 is used. The viscosity measurement is recorded after
15 seconds at 23.degree. C. The spindle is cleaned between
measurements. Brookfield viscosity is measured at 100 rpm and is
reported in centipoise (cP).
[0179] Unit Weight (i.e., the weight of the fabric per square
meter) is measured by cutting a "0.254 m.times.0.127 m" sample of
fabric and weighing the fabric using an analytical balance in
grams. Then, the unit weight is calculated by dividing the measured
weight by the area and the result is reported in grams per square
meter (g/m.sup.2).
[0180] Coat weight is measured by weighing the dried coated fabric
using an analytical balance in grams, and determining the
difference between the weight of the polyester fabric and the
weight of the dried coated fabric. Then, the coat weight is
calculated by dividing the measured weight difference by the areas
and the result is reported in grams per square meter
(g/m.sup.2).
[0181] Tensile strength at break is measured according to ASTM
D638, and is reported in megaPascals (MPa).
[0182] Elongation at break is measured in accordance with ASTM
D638, and is reported in percent (%).
[0183] Shore A Hardness is measured in accordance with ASTM
D2240.
[0184] Primer pot-life is determined by measuring the time between
combination of a crosslinking agent (such as DESMODUR.TM. RFE) with
a mixture containing a polymeric component and a solvent, and when
the combination begins to gel. Onset of gel is visually determined.
Primer pot-life is measured in hours.
[0185] Solution viscosity is measured in a 20% toluene solution at
25.degree. C., in accordance with BAM 922, and is reported in
millipascal-seconds (mPas).
[0186] Differential Scanning Calorimetry
[0187] Differential Scanning calorimetry (DSC) can be used to
measure the melting and crystallization behavior of a polymer over
a wide range of temperature. For example, the TA Instruments Q1000
DSC, equipped with an RCS (refrigerated cooling system) and an
autosampler is used to perform this analysis. During testing, a
nitrogen purge gas flow of 50 ml/min is used. Each sample is melt
pressed into a thin film at about 175.degree. C.; the melted sample
is then air-cooled to room temperature (about 25.degree. C.). A
3-10 mg, 6 mm diameter specimen is extracted from the cooled
polymer, weighed, placed in a light aluminum pan (ca 50 mg), and
crimped shut. Analysis is then performed to determine its thermal
properties.
[0188] The thermal behavior of the sample is determined by ramping
the sample temperature up and down to create a heat flow versus
temperature profile. First, the sample is rapidly heated to
180.degree. C. and held isothermal for 3 minutes in order to remove
its thermal history. Next, the sample is cooled to -40.degree. C.
at a 10.degree. C./minute cooling rate and held isothermal at
-40.degree. C. for 3 minutes. The sample is then heated to
180.degree. C. (this is the "second heat" ramp) at a 10.degree.
C./minute heating rate. The cooling and second heating curves are
recorded. The cool curve is analyzed by setting baseline endpoints
from the beginning of crystallization to -20.degree. C. The heat
curve is analyzed by setting baseline endpoints from -20.degree. C.
to the end of melt. The values determined are extrapolated onset of
melting, Tm, and extrapolated onset of crystallization, Tc. Heat of
fusion (H.sub.f) (in Joules per gram), and the calculated %
crystallinity for polyethylene samples using the following
Equation: % Crystallinity=((H.sub.f)/292 J/g).times.100.
[0189] The heat of fusion (H.sub.f) and the peak melting
temperature are reported from the second heat curve. Peak
crystallization temperature is determined from the cooling
curve.
[0190] Melting point, Tm, is determined from the DSC heating curve
by first drawing the baseline between the start and end of the
melting transition. A tangent line is then drawn to the data on the
low temperature side of the melting peak. Where this line
intersects the baseline is the extrapolated onset of melting (Tm).
This is as described in Bernhard Wunderlich, The Basis of Thermal
Analysis, in Thermal Characterization of Polymeric Materials 92,
277-278 (Edith A. Turi ed., 2d ed. 1997).
[0191] Crystallization temperature, Tc, is determined from a DSC
cooling curve as above except the tangent line is drawn on the high
temperature side of the crystallization peak. Where this tangent
intersects the baseline is the extrapolated onset of
crystallization (Tc).
[0192] Some embodiments of the present disclosure will now be
described in detail in the following Examples.
EXAMPLES
[0193] Materials used to produce the primer compositions and
articles are provided in Table 1 below.
TABLE-US-00001 TABLE 1 Starting materials. Component Specification
Source LOTADER .TM. AX8900 ethylene/methyl acrylate/glycidyl
methacrylate random terpolymer Arkema (EMA/GMA) methyl acrylate
content = 24 wt % glycidyl methacrylate content = 8 wt % melt index
= 6 g/10 min (190.degree. C./2.16 kg) melting point = 65.degree. C.
density = 0.94 g/cc LOTADER .TM. 4700 ethylene/ethyl
acrylate/maleic anhydride random terpolymer Arkema (EEA/MAH) ethyl
acrylate content = 29 wt % maleic anhydride content = 1.3 wt % melt
index = 7 g/10 min (190.degree. C./2.16 kg) melting point =
65.degree. C. density = 0.94 g/cc OREVAC .TM. T 9305 ethylene/vinyl
acetate/maleic anhydride random terpolymer Arkema (EVA/MAH) vinyl
acetate content = 26-30 wt % maleic anhydride content = 0.64 wt %
melt index = 150-210 g/10 min (190.degree. C./2.16 kg) melting
point = 68.degree. C. density = 0.951 g/cc Michem .TM. Prime
aqueous dispersion of ethylene/acrylic acid copolymer Michelman,
Inc. 4983R (EAA) non-volatile solids = 24.2-25.4% pH = 8.4-9.4
HARDLEN .TM. F-2P chlorinated polyolefin modified with maleic
anhydride TOYOBO Co., (Cl-PO) chlorine content = 20 wt % Ltd.
solution viscosity = 60 mPa s (in a 20% toluene solution at
25.degree. C., in accordance with BAM 922) Kraton .TM. FG 1901G
maleic anhydride grafted styrene/ethylene butylene/styrene
copolymer Kraton (MAH-g-SEBS) maleic anhydride content = 1.4-2.0 wt
% polystyrene content = 30 wt % melt flow = 22 g/10 min
(230.degree. C./5 kg) density = 0.91 g/cc HYPOD .TM. 1001
carboxylated propylene copolymer dispersion in water The Dow
(COO-PP) solids content = 40-44% Chemical pH = 9.0-10.5 Company
Brookfield Viscosity = <500 cP melting point = 85.degree. C.
VESTOPLAST .TM. W- water-based dispersion of amorphous alpha
polyolefin Evonik 1750 solids content = 47% Industries (APAO) pH =
9.5 Brookfield Viscosity at 20.degree. C. = 450 mPa s DESMODUR .TM.
RFE polyisocyanate crosslinking agent Bayer (27/73 blend) 27 wt %
tris (p-isocyanatophenyl) thiophosphate (isocyanate compound)
MaterialScience 73 wt % ethyl acetate (polar solvent) Solvent
toluene Sigma-Aldrich Solvent methyl cyclohexane Sigma-Aldrich
Solvent methyl ethyl ketone Sigma-Aldrich PET Closed Mesh closed
mesh Category 2 architecture fabric, woven Panama weave 2/2 Fabric
Substrate untreated unit weight = 271 g/m.sup.2 1100 dTex (mass in
grams per 10,000 m, yarn specification) INFUSE .TM. 9010
ethylene/octene multi-block copolymer The Dow melt index = 0.50
g/10 min (190.degree. C./2.16 kg) Chemical melting point =
122.degree. C. Company density = 0.879 g/cc Shore A = 77 tensile
strength at break = .gtoreq.13.2 MPa elongation at break =
.gtoreq.750% Magnifin .TM. H-5 MV filler (magnesium hydroxide
(MDH)) Albemarle density = 2.4 g/cc Irganox .TM. B 225 Antioxidant
blend BASF pentaerythritol
tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and
tris(2,4-ditert-butylphenyl)phosphite Chimassorb .TM. 2020 hindered
amine light stabilizer (HALS) BASF
1. Preparation of Primer Compositions
[0194] A given amount of solvent is weighed into a 2 L, 3-necked,
round-bottom glass flask in a hood. After attaching a reflux
condenser and an over-head mechanical stirrer, ethylene acrylate
polymer containing maleic anhydride or glycidyl methacrylate (or
comparative polymer) is added to the flask under a slow agitation,
to form a primer composition with a solids content of 12-50 wt %.
The primer composition is mixed in a Speedy Mixer at a speed of
3000 rpm for 30 seconds at 60.degree. C.
[0195] To prepare Example 1A (Ex. 1A) and Comparative Samples 4A,
8A and 9A (CS 4A, CS 8A, and CS 9A) of Table 2,10 g of the
above-made primer composition is weighed into a glass vial. Then, a
given amount of a polyisocyanate crosslinking agent (DESMODUR.TM.
RFE) is added and mixed by a spatula for 3 to 5 minutes to make a
uniform mixture.
[0196] Example 2A (Ex. 2A) and Comparative Samples 3A and 5A-7A
(CS3A, and CS5A, CS7A) of Table 2 each is void of a crosslinking
agent.
[0197] Table 2 provides the formulation for each primer
composition.
2. Preparation of Coated Closed Mesh PET Fabric Article
[0198] The closed mesh PET fabric roll is inserted into a roller
coating line (a KTF-S line from Mathis AG), where the closed mesh
PET fabric roll is roller coated with the above-made Example and
Comparative Sample primer compositions. The closed mesh PET fabric
coated with a primer composition is dried in an oven at 100.degree.
C. for three minutes to form an adhesive layer on the closed mesh
PET fabric (a PET fabric/adhesive layer structure). The coat weight
is measured. A typical coat weight is approximately 10-45 g/m.sup.2
(after drying). Only one side of the closed mesh PET fabric is
coated. The coat weight of each Example and Comparative Sample
adhesive layer (dried primer composition) applied to the closed
mesh PET fabric is provided in Table 2.
[0199] A control sample (CS10) is prepared without a primer
composition on the closed mesh PET fabric.
3. Preparation of Filled Olefin Block Copolymer (OBC)
[0200] INFUSE.TM. 9010 ethylene/octene multi-block copolymer (OBC),
Magnifin.TM. H-5 MV (magnesium hydroxide (MDH)), titanium dioxide
(TiO.sub.2), Irganox.TM. B 225, and Chimassorb2020.TM. are weighed
into a Kraus Maffei twin screw lab line extruder, and blended in
the extruder to form a filled OBC composition. The filled OBC
composition contains 35 wt % INFUSE.TM. 9010 OBC, 60 wt % MDH, 0.5
wt % TiO.sub.2, 0.2 wt % Irganox.TM. B 225, and 0.4 wt % Chimassorb
2020.
4. Preparation of PET Fabric/Adhesive Layer/Filled OBC Layer
Article
[0201] The coated closed mesh PET fabrics prepared as described
above are rolled with a Mathis Ag KTF-S automated line. Each rolled
coated closed mesh PET fabric is placed in a calendar extrusion
line with the extruder containing the filled OBC composition. The
filled OBC composition is extruded onto the coating of the coated
closed mesh PET fabric at an extrusion temperature of 270.degree.
C., to form a PET fabric/adhesive layer/filled OBC layer article.
The PET fabric/adhesive layer/filled OBC layer article passes
through a series of 3 vertical calendar rolls. After passing
through the calendar rolls, the final PET fabric/adhesive
layer/filled OBC layer article has a thickness of 1-1.5 mm.
[0202] The control sample (CS 10) is prepared without a primer
composition on the closed mesh PET fabric.
5. Adhesion Testing--T-Peel Test
[0203] The PET fabric/adhesive layer/filled OBC article is cut into
"2.45 cm.times.15.24 cm" strips (each strip had a bond area of
"2.45 cm.times.12.7 cm") and conditioned at 23.degree. C. and a
relative humidity of 40% to 50% for 24 hours for the T-peel
adhesion test. A TA XT Plus Texture Analyzer from Stable
Microsystems is used to peel apart the closed mesh PET fabric and
the filled OBC layer at room temperature (23.degree. C.), at speed
of 5.08 cm/min, and grip distance of 20 mm. The release liner is
removed from each strip, and the free ends of the test sample are
inserted into the clamps of the test machine. The average peel
strength (Newtons per centimeter (N/cm)) is determined from the
force versus distance profile. Two or three test samples are tested
and the average "average peel strength" is reported. The adhesion
between the closed mesh PET fabric and the filled OBC layer with
various primer compositions applied between the closed mesh PET
fabric and filled OBC layer is provided in Table 2.
[0204] Adhesion is visually rated on a scale of 1 to 4. A rating of
1 indicates the closed mesh PET fabric cannot be separated from the
filled OBC layer. A rating of 2 indicates slight separation. A
rating of 3 indicates intermediate separation. A rating of 4
indicates the closed mesh PET fabric can be separated from the
filled OBC layer with manual (i.e., hand) peeling. Samples with a
rating of 1 or 2 meet customer requirements for adhesion (i.e.,
have a peel strength greater than 12 N/cm), while samples with a
rating of 3 or 4 do not meet customer requirements for adhesion
(i.e., have a peel strength less than 12 N/cm). Adhesion rating is
provided in Table 2.
[0205] In Table 2, primer compositions are denoted with the letter
"A," closed mesh PET fabrics coated with primer composition and
dried (i.e., coated closed mesh PET fabric articles) are denoted
with the letter "B," and PET fabric/adhesive layer/filled OBC layer
articles formed from filled OBC and the closed mesh PET fabrics
coated with primer composition and dried are denoted with the
letter "C." By way of explanation, coated closed mesh PET fabric
Ex. 1B is coated with primer composition Ex. 1A and dried, and PET
fabric/adhesive layer/filled OBC layer article Ex. 1C includes the
filled OBC and coated closed mesh PET fabric Ex. 1B--thus, Ex. 1
constitutes Ex. 1A, Ex. 1B, and Ex. 1C.
TABLE-US-00002 TABLE 2 Primer Compositions and
Articles.sup..diamond. Ex 1 Ex 2 CS 3 CS 4 CS 5 CS 6 CS 7 CS 8 CS 9
CS 10 Primer Compositions Ex 1A Ex 2A CS 3A CS 4A CS 5A CS 6A CS 7A
CS 8A CS 9A CS 10A LOTADER .TM. AX8900 11.7 -- -- -- -- -- -- -- --
-- (EMA/GMA) OREVAC .TM. T 9305 -- 12 -- -- -- -- -- -- -- --
(EVA/MAH) LOTADER .TM. 4700 -- -- 12 -- -- -- -- -- -- -- (EEA/MAH)
Michem .TM. Prime 4983R -- -- -- -- 25 -- -- -- -- -- (EAA) HARDLEN
.TM. F-2P -- -- -- 9.75 -- -- -- 8.55 8.55 -- (Cl-PO) Kraton .TM.
FG 1901G -- -- -- 9.75 -- -- -- 8.55 8.55 -- (MAH-g-SEBS) HYPOD
.TM. 1001 -- -- -- -- -- 40 -- -- -- -- (COO-PP) VESTOPLAST .TM.
W-1750 -- -- -- -- -- -- 50 -- -- -- (APAO) Toluene 88 88 88 -- --
-- -- -- -- -- Methyl Cyclohexane -- -- -- 80 -- -- -- 82 82 --
Methyl Ethyl Ketone -- -- -- -- -- -- -- -- -- -- DESMODUR RFE* 0.3
-- -- 0.5 -- -- -- 0.9 0.9 -- Total Primer (wt %) 100 100 100 100
100 100 100 100 100 0 Primer Solids Content (wt %) 12 12 12 20 25
40 50 18 18 N/A Primer Brookfield Viscosity (cP) 230 74 240 770 985
460 1760 780 780 N/A Primer Pot-Life (hours) >4 >4 >4
<0.5 >4 >4 >4 1 1 N/A Coated Closed Mesh PET Fabric Ex
1B Ex 2B CS 3B CS 4B CS 5B CS 6B CS 7B CS 8B CS 9B CS 10B Primer
Coat Weight after 10-15 10-15 10-15 15-20 20 35-45 35-45 15-20
15-20 N/A Drying (g/m.sup.2) PET Fabric/Adhesive Layer/Filled OBC
Layer Ex 1C Ex 2C CS 3C CS 4C CS 5C CS 6C CS 7C CS 8C CS 9C CS 10C
Peel Strength (N/cm) 16 20 5 18 5 5 5 21 18 5 Adhesive Rating.sup.#
1 2 4 1-2 4 4 4 1 1 4 CS = Comparative Sample N/A = Not Applicable
.sup..diamond.Weight percents are based on the total weight percent
of the primer compositions. *DESMODUR RFE is added as a solution
containing 27 wt % tris (p-isocyanatophenyl) thiophosphte and 73 wt
% ethyl acetate (a solvent), based on the combined amount of tris
(p-isocyanatophenyl) thiophosphate and ethyl acetate components.
.sup.#Adhesive Rating is visually determined on a scale of 1 to 4.
A rating of 1 indicates the closed mesh PET fabric cannot be
separated from the filled OBC layer. A rating of 2 indicates slight
separation. A rating of 3 indicates intermediate separation. A
rating of 4 indicates the closed mesh PET fabric can be separated
from the filled OBC layer with manual (i.e., hand) peeling.
6. Results and Discussion
[0206] As shown, halogen-free articles formed from (A) a closed
mesh PET fabric, (B) an adhesive layer containing (i) an EVA/MAH
terpolymer or (ii) an EMA/GMA terpolymer crosslinked with a
polyisocyanate, and (C) an outer layer containing OBC and filler
(Ex. 1 and Ex. 2) advantageously exhibit a peel strength of greater
than 12 N/cm (Ex. 1 has a peel strength of 16 N/cm and Ex. 2 has a
peel strength of 20 N/cm), which is a comparable peel strength (as
measured by the T-Peel Test described above) to halogenated
articles in which the coating contains a chlorinated polyolefin and
a maleic anhydride grafted styrene/ethylene butylene/styrene
copolymer (CS 4, CS 8, CS 9).
[0207] Moreover, halogen-free articles formed from (A) a closed
mesh PET fabric, (B) an adhesive layer containing (i) an EVA/MAH
terpolymer or (ii) an EMA/GMA terpolymer crosslinked with a
polyisocyanate, and (C) an outer layer containing OBC and filler
(Ex. 1 and Ex. 2) advantageously exhibit a peel strength of greater
than 12 N/cm (Ex. 1 has a peel strength of 16 N/cm and Ex. 2 has a
peel strength of 20 N/cm), which is an improved peel strength over
(i.e., higher than) a comparative article in which the coating
contains ethylene/acrylic acid copolymer (CS 5, having a peel
strength of 5 N/cm), carboxylated propylene copolymer (CS 6, having
a peel strength of 5 N/cm), or amorphous alpha polyolefin (CS 7,
having a peel strength of 5 N/cm). Further, a comparative article
in which the coating contains ethylene/ethyl acrylate/maleic
anhydride terpolymer (EEA/MAH terpolymer) (CS 3) exhibits a peel
strength of 5 N/cm, which is insufficient to meet industry
requirements for adhesion (industry requirements being a peel
strength of greater than 12 N/cm). None of CS 3, CS 5, CS 6, CS 7
or CS 10 meet industry requirements for adhesion because they each
exhibit a peel strength of less than 12 N/cm.
[0208] It is specifically intended that the present disclosure not
be limited to the embodiments and illustrations contained herein,
but include modified forms of those embodiments including portions
of the embodiments and combinations of elements of different
embodiments as come within the scope of the following claims.
* * * * *