Europäisches Patentamt

(19) European Patent Office *EP001254766A1*

Office européen des brevets (11) EP 1 254 766 A1
(12) EUROPEAN PATENT APPLICATION

(43) Date of publication: (51) Int Cl.7: B32B 27/08, B32B 27/20
06.11.2002 Bulletin 2002/45

(21) Application number: 02009310.0

(22) Date of filing: 30.04.2002

(84) Designated Contracting States: (72) Inventors:

AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU • Hale, Wesley Raymond
MC NL PT SE TR Kingsport, Tennessee 37663 (US)
Designated Extension States: • Germroth, Ted Calvin
AL LT LV MK RO SI Kingsport, Tennessee 37664 (US)

(30) Priority: 01.05.2001 US 287876 P (74) Representative:

25.01.2002 US 56778 Wibbelmann, Jobst, Dr., Dipl.-Chem.
Wuesthoff & Wuesthoff,
(71) Applicant: EASTMAN CHEMICAL COMPANY Patent- und Rechtsanwälte,
Kingsport, TN 37660 (US) Schweigerstrasse 2
81541 München (DE)

(54) Multilayer films

(57) There are provided novel multilayer films com- or different. The multilayer films are preferably charac-
prising a layer comprising a thermoplastic polymer, such terized by having increased moisture vapor transmis-
as an aliphatic-aromatic copolyester (AAPE), with or sion rate (MVTR). Also provided are novel articles of
without filler, and a layer comprising a filled thermoplas- manufacture comprising the novel multilayer films.
tic polymer. The polymers in the layers may be the same
EP 1 254 766 A1

Printed by Jouve, 75001 PARIS (FR)

 EP 1 254 766 A1

Description

FIELD OF THE INVENTION

5 [0001] This invention relates to multilayer films that are characterized by preferably having increased moisture vapor
transmission rates (MVTR).

BACKGROUND OF THE INVENTION

10 [0002] Stretching of properly formulated films that are fabricated from polyolefins filled with solid particles (e.g., a
mineral such as calcium carbonate), under appropriate conditions, is known to create porous structures that allow for
the diffusion of water vapor while providing liquid barrier. This is a desirable property in markets such as hygienics,
industrial and medical. Indeed, a major consideration in the comfort of a garment is its ability to maintain a balance
between heat production and heat loss. The loss of heat through clothing may occur through direct dry heat loss or by
15 moisture evaporation. In respect to the latter, the moisture vapor transmission rate of the material utilized in forming
the garment is generally related to the breathability of the material. Breathability is the ability to diffuse moisture/water
vapor through a film or garment. In addition to this property, there are many applications requiring that the material
used in preparing the garment be impermeable to a liquid. Such applications include diaper back sheets, sanitary
napkins, medical protective garments, surgical incise drapes, transdermal patches, wound care bandages and dress-
20 ings, intravenous site dressings, ostomy site dressings, breathable construction films such as housewrap, among oth-
ers. In general, porous films do not provide a sufficient barrier to bacteria and/or virus, or to wind.
[0003] Films, which are permeable to water vapor and are porous but yet are intended to be impermeable to a liquid,
are described in U.S. Patent Nos. 4,626,252 and 5,073,316. As disclosed, a porous film is obtained by mixing a poly-
olefin resin, an inorganic filler and a plasticizer; forming a film from the mixture; and uniaxially or biaxially stretching
25 the film. Films of this type are also disclosed in U.S. Patent No. 5,998,505 and PCT International Application Publication
No. WO 98/05501.
[0004] Examples of multilayer breathable films are described in the following U.S. patents.
[0005] U.S. Patent No. 6,114,024 describes a method of making a stretched, multilayer breathable film having at
least 5 layers that is a barrier to bacteria. The outer layer is made of a non porous, non filler containing breathable
30 polymer to provide bacteria barrier and to extend the process time by protecting the extruder die from build up of the
filler contained in its most inner layer. This method teaches the need for microporous tie layers between the outer non-
porous, non-filler containing layers and the inner filler-containing layer.
[0006] U.S. Patent No. 5,164,258 describes a multilayer breathable film consisting of outer layers of a breathable
hydrophobic material (microporous), a core hygroscopic barrier layer (monolithic), and adhesive layers disposed be-
35 tween the core layer and the two outer layers. This patent teaches the use of filled, unstretched polyolefins as structural
support as outer layers for an inner oxygen barrier layer during steam sterilization. During steam sterilization the inner
layer absorbs large amounts of water reducing its barrier to oxygen. The breathable outer layers described allow for
the desorption of water from the inner layer, thus recovering the package oxygen barrier.
[0007] U.S. Patent No. 5,143,773 discloses a multilayer film consisting of a water absorbing central layer (monolithic)
40 with a humoctant (water absorbing material) having on one side a water impermeable, non-porous, non-breathable
layer and on another side a microporous layer. This multilayer film is useful for packaging water sensitive materials
where the relative humidity inside the package must be controlled.
[0008] U.S. Patent No. 4,828,556 discloses multilayer breathable film consisting of a polyvinyl alcohol monolithic
layer between two microporous non-woven web layers.
45 [0009] U.S. Patent No. 4,863,788 discloses a multilayer film consisting of a microporous membrane having on one
side a continuous film protective layer and on another side a cellular foam adhesive layer and a fabric substrate.
[0010] U.S. Patent No. 4,758,239 discloses a multilayer breathable film consisting of a water-soluble polymeric layer
having on one side a microporous sheet.

50 SUMMARY OF THE INVENTION

[0011] It is accordingly an object of the present invention to provide new and improved multi-layer films.
[0012] It is a further object of this invention to provide novel multi-layer films, which preferably are characterized by
having improved moisture vapor transmission rates (MVTR).
55 [0013] These and other objects and advantages of the present invention will be apparent to those skilled in the art
from the following detailed description and claims.
[0014] In accordance with the present invention, it has been found that the above and still further objects are achieved
by providing, in a first embodiment, a multilayer film comprising:

2
 EP 1 254 766 A1

(a) a first layer comprising from about 70 to 100 weight percent of at least one or more thermoplastic polymer(s)
having a MVTR value of at least 300 g-µm/m2-hour, as determined in accordance with ASTM Test Method E-96D,
and from 0 to about 30 weight percent filler, and
(b) a second layer comprising from about 20 to about 80 weight percent of at least one or more thermoplastic
5 polymer(s) and from about 20 to about 80 weight percent filler and the second layer having in stretched form a
MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM E-96D, of the at least
one or more thermoplastic polymer(s) of the second layer,

wherein the second layer comprises an amount of filler differing from the amount of filler in the first layer when the at
10 least one or more thermoplastic polymer(s) of the first layer and the at least one or more thermoplastic polymer(s) of
the second layer are the same, wherein the first layer is adjacent to the second layer, and wherein the multilayer film,
in stretched form, has a MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM
E-96D, of the at least one or more thermoplastic polymer(s) of the first layer.
[0015] In a second embodiment of the present invention, there is provided a multilayer film comprising:
15
(a) a first layer comprising

(i) from about 70 to 100 weight percent of at least one or more linear or branched or chain extended, random,
aliphatic-aromatic copolyester(s) having a MVTR value of at least 300 g-µm/m2-hour or g-mil/m2-day, as de-
20 termined in accordance with ASTM Test Method E-96D, and comprising repeating units of:

25

30

wherein

35 R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole
percent of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene
or oxylalkylene substituted with one to four substituents independently selected from the group consisting
of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C12 cycloalkylene (for example, 1,4-cyclohexanedimethanol);
40 C5-C12 cycloalkylene substituted with one to four substituents independently selected from the group con-
sisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene
or oxylalkylene substituted with one to four substituents independently selected from the group consisting
of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one
45 to four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4
alkoxy; and the mole percent of R2 is from about 35 to about 95;
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one
to four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4
alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently
50 selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is
from about 5 to about 65; and

(ii) from 0 to about 30 weight percent filler, and

55 (b) a second layer having in stretched form a MVTR value, according to ASTM E-96D, of at least about 500 g-µm/
m2-hour or g-mil/m2-day, and comprising

(i) from about 20 to about 65 weight percent of at least one or more thermoplastic polymer(s) selected from

3
 EP 1 254 766 A1

the group consisting of a polyolefin and the linear or branched or chain extended, random, aliphatic-aromatic
copolyester of the first layer and
(ii) from about 35 to about 80 weight percent filler;

5 wherein the first layer is adjacent to the second layer and wherein the multilayer film, in stretched form, has a
MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM E-96D, of the at least
one or more linear or branched or chain extended, random, aliphatic-aromatic copolyester(s) of the first layer.

[0016] Additionally, the present invention is directed to articles of manufacture incorporating the novel films of the
10 present invention. Such articles include garments, diapers, sanitary napkins, medical protective garments, surgical
incise drapes, transdermal patches, wound care bandages and dressings, intravenous site dressings, and ostomy site
dressings, house wrap, and others, incorporating the novel films of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

15
[0017] In accordance with the present invention, it has been found that the above and still further objects are achieved
by providing, in a first embodiment, a multilayer film comprising:

(a) a first layer comprising from about 70 to 100 weight percent of at least one or more thermoplastic polymer(s)
20 having a MVTR value of at least 300 g-µm/m2-hour, as determined in accordance with ASTM Test Method E-96D,
and from 0 to about 30 weight percent filler, and
(b) a second layer comprising from about 20 to about 80 weight percent of at least one or more thermoplastic
polymer(s) and from about 20 to about 80 weight percent filler and the second layer having in stretched form a
MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM E-96D, of the at least
25 one or more thermoplastic polymer(s) of the second layer,

wherein the second layer comprises an amount of filler differing from the amount of filler in the first layer when the at
least one or more thermoplastic polymer(s) of the first layer and the at least one or more thermoplastic polymer(s) of
the second layer are the same, wherein the first layer is adjacent to the second layer, and wherein the multilayer film,
30 in stretched form, has a MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM
E-96D, of the at least one or more thermoplastic polymer(s) of the first layer.
[0018] Preferably, the multilayer film in stretched form has a MVTR value greater than about 500 to about 10,000 g-
µm/m2-hour. The more common unit of measure for MVTR is "g-mil/m2-day". The conversion of g-µm/m2-hour to g-
mil/ m2-day is approximately one-to-one. Thus, all MVTR values herein are shown as either unit of measure.
35 [0019] Additionally, the present invention is directed to articles of manufacture incorporating the novel films of the
present invention. Such articles include garments, diapers, sanitary napkins, medical protective garments, surgical
incise drapes, transdermal patches, wound care bandages and dressings, intravenous site dressings, and ostomy site
dressings, house wrap, and others, incorporating the novel films of the present invention.
[0020] In preparing the multilayer films of the present invention, there may be used in the first layer any thermoplastic
40 polymer having a MVTR value of at least 300 to about 10,000 g-µm/m2-hour or g-mil/m2-day, preferably from about
300 to about 3000 g-µm/m2-hour or g-mil/m2-day, as determined in accordance with ASTM E-96D. Examples are
thermoplastic polymers of the following groups that have a MVTR value of at least 300 to about 10,000 g-µm/m2-hour
or g-mil/m2-day. The groups include linear or branched or chain extended aliphatic-aromatic copolyesters, polylactic
acid (PLA) polymers and copolymers, polyurethanes, polyhydroxybutyrate and poly hydroxybutyrate and other poly-
45 hydroxybutyrate copolymers with co-monomers such as valeric acid and gaµma hydroxy alkanoates, polyesteramides
(such as BAK™ polymers produced by Bayer), poly vinyl alcohol, cellulose esters, polycaproyl lactone (PCL) polymers
and copolymers, HYTREL™ copolymers of for example terephthalic acid, isophthalic acid, with various diols (e.g.
butane diol) and polytetramethylene glycol or polypropylene glycol produced by DuPont, PEBAX™ polyether amides
with polyethylene glycol produced by Ato-Chem, SYMPATEX™ polyethylene glycol modified polybutylene terephtha-
50 late produced by Akzo, and various polyether urethanes, or blends thereof.
[0021] The aliphatic-aromatic copolyesters of the present invention (referred to as AAPE herein) include those de-
scribed in U.S. Patent Nos. 5,661,193; 5,599,858; 5,580,911; and 5,446,079. The entire disclosures of each patent
are herein incorporated by reference. More specifically, the AAPEs are essentially, linear, random copolyesters or
branched and/or chain extended copolyesters thereof having repeating units of:
55

4
 EP 1 254 766 A1

10

wherein

R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole percent
15 of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene or
oxylalkylene substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; C5-C12 cycloalkylene (for example, 1,4-cyclohexanedimethanol); C5-C12 cy-
cloalkylene substituted with one to four substituents independently selected from the group consisting of halo,
20 C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene or
oxylalkylene substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents
independently selected from the group consisting of halo, C6-C10) aryl, and C1-C4 alkoxy; and the mole percent
25 of R2 is from about 35 to about 95;
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one to four
substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10
cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently selected from the group
consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is from about 5 to about 65.
30 Preferred AAPEs are those wherein R1 is selected from C2-C8 alklyene and is present in an amount of from
about 90 to 100 mole percent; R3 is present in an amount of from 0 to about 10 mole percent; R2 is selected from
one or more of the groups consisting of C2-C8 alkylene or oxyalkylene and is present in an amount from about 35
to about 95 mole percent; and R4 is selected from one or more of the groups consisting of C6-C10 aryl and is
present in an amount of from about 5 to about 65 mole percent. More preferred AAPEs are those wherein R1 is
35 selected from C2-C4 alklyene and is present from about 95 to 100 mole percent; R3 is present from 0 to about 5
mole percent; R2 is selected from one or more of the groups consisting of C2-C6 alkylene or C2 oxyalkylene and
is present from about 35 to about 65 mole percent; R4 is 1,4-disubstituted-C6 aryl and is present from about 35 to
about 65 mole percent.

40 [0022] As used herein the terms "alkyl" and "alkylene" refer to either straight or branched chain moieties such as -
CH2 - CH2- CH2- CH2-and-CH2CH(X) - CH2 -. The term "oxyalkylene" refers to alkylene chains containing from 1 to 4
ether oxygen groups. The term "cylcoalkylene" refers to any alkyl group that contains a cycloalkyl moiety.
[0023] Other preferred compositions for these AAPE are those prepared from the following diols and diacids (or
polyester forming derivatives thereof) in the following mole percent, based on 100 mole percent of a diacid component
45 and 100 mole percent of a diol component:

(1) glutaric acid (about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to
100%); and modifying diol (0 about 10%).
(2) succinic acid (about 30 to about 95%); terephthalic acid (about 5 to about 70%); 1,4-butanediol (about 90 to
50 100%); and modifying diol (0 to about 10%).
(3) adipic acid (about 30 to about 75%); terephthalic acid (about 25 to about 70%); 1,4-butanediol (about 90 to
100%); and modifying diol (0 to about 10%).

[0024] The modifying diol is preferably selected from 1,4-cyclohexanedimethanol, triethylene glycol, polyethylene
55 glycol and neopentyl glycol. The most preferred AAPEs are linear, branched or chain extended copolyesters comprising
about 50 to about 60 mole percent adipic acid, about 40 to about 50 mole percent terephthalic acid, and at least 95
mole percent 1,4-butanediol. Even more preferably, the adipic acid is present from about 55 to about 60 mole percent,
the terephthalic acid is present from about 40 to about 45 mole percent and at least 95 mole percent 1,4-butanediol.

5
 EP 1 254 766 A1

Such compositions are coµmercially available from Eastman Chemical Company, Kingsport, TN.
[0025] Specific examples of preferred AAPE include a poly(tetramethylene glutarate-co-terephthalate) containing
(a) 50% glutaric acid/50% terephthalic acid/100% 1,4-butanediol, (b) 60% glutaric acid/40% terephthalic acid/100%
1,4-butanediol or (c) 40% glutaric acid/60% terephthalic acid/100% 1,4-butanediol; a poly(tetramethylene succinate-
5 co-terephthalate) containing (a) 85% succinic acid/15% terephthalic acid/100% 1,4-butanediol or (b) 70% succinic
acid/30% terephthalic acid/100% 1,4-butanediol; a poly(ethylene succinate-co-terephthalate) containing 70% succinic
acid/30% terephthalic acid/100% ethylene glycol; and a poly(tetramethylene adipate-co-terephthalate) containing 85%
adipic acid/15% terephthalic acid/100 % 1,4-butanediol.
[0026] Desirably, the AAPE has from about 10 to about 1,000 repeating units and preferably, from about 15 to about
10 600 repeating units. Preferably, the AAPE has an inherent viscosity of about 0.4 to about 2.0 dL/g, more preferably
about 0.7 to about 1.4, as measured at a temperature of 25° C. for a 0.5 gram sample in 100 ml of a 60/40 by weight
solution of phenol/tetrachloroethane.
[0027] The AAPE of the present invention may also contain a branching agent. The weight percent ranges for the
branching agent are from about 0.01 to about 10 percent, preferably 0.1 to 1.0 weight percent, based on the total
15 weight percent of the AAPE.
[0028] The branching agent preferably has a weight average molecular weight of about 50 to about 5000, more
preferably about 92 to about 3000, and a functionality of about 3 to about 6. The branching agent may be a polyol
having 3 to 6 hydroxyl groups, a polycarboxylic acid having 3 or 4 carboxyl groups or a hydroxy acid having a total of
3 to 6 hydroxyl and carboxyl groups.
20 [0029] Representative low molecular weight polyols that function as branching agents include glycerol, trimethylol-
propane, 1,2,4-butanetriol, pentaerythritol, 1,2,6-hexanetriol, sorbitol, 1,1,4,4,-tetrakis (hydroxymethyl) cyclohexane,
tris(2-hydroxyethyl) isocyanurate, and dipentaerythritol. Particular branching agent examples of higher molecular
weight polyols (MW 400-3000) are triols derived by condensing alkylene oxides having 2 to 3 carbons, such as ethylene
oxide and porpylene oxide with polyol initiators.
25 [0030] Representative polycarboxylic acids that may be used as branching agents include hemimellitic acid, trimellitic
acid, trimesic acid, pyromellitic acid, benzene tetracarboxylic acid, benzophenone tetracarboxylic acid, 1,1,2,2-ethan-
etetracarboxylic acid, 1,1,2-ethanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, and 1,2,3,4-cyclopentanetetra-
carboxylic acid. Although the acids may be used as such, preferably they are used in the form of their lower alkyl esters
or their cyclic anhydrides in those instances where cyclic anhydrides can be formed.
30 [0031] Representative hydroxy acids as branching agents include malic acid, citric acid, tartaric acid, 3-hydroxyglu-
taric acid, mucic acid, trihydroxyglutaric acid, and 4-(beta-hydroxyethyl)phthalic acid. Such hydroxy acids contain a
combination of 3 or more hydroxyl and carboxyl groups.
[0032] Especially preferred branching agents include trimellitic acid, trimesic acid, pentaerythritol, trimethylol propane
and 1,2,4-butanetriol.
35 [0033] One example of the branched AAPE of the present invention is poly(tetramethylene adipate-co-terephthalate)
containing 100 mole percent 1,4-butanediol, 43 mole percent terephthalic acid and 57 mole percent adipic acid and
being branched with 0.5 weight percent pentaerythritol. This copolyester is produced when dimethyladipate, dimethyl
terephthalate, pentaerythritol and 1,4-butanediol are heated at 190° C. for 1 hour, 200° C. for 2 hours, 210° C. for 1
hour, then at 250° C. for 1.5 hours under vacuum in the presence of 100 ppm of Ti present initially as Ti(OiPr)4. The
40 copolyester is typically pelletized after formation for use in extrusion foaming.
[0034] Another branched AAPE of the present invention is poly(tetramethylene adipate-co-terephthalate) containing
100 mole percent 1,4-butanediol, 43 mole percent terephthalic acid and 57 mole percent adipic acid and being branched
with 0.3 weight percent pyromellitic dianhydride. This copolyester is produced via reactive extrusion of linear poly
(tetramethylene adipate-co-terephthalate) with pyromellitic dianhydride using an extruder.
45 [0035] The AAPE of the present invention may also contain a chain extender. Exemplary chain extenders are divinyl
ethers as disclosed in U.S. Pat. No. 5,817,721 and herein incorporated by reference. Preferred divinyl ethers are
1,4-butanediol divinyl ether, 1,5-hexanediol divinyl ether and 1,4-cyclohexandimethanol divinyl ether. The weight per-
cent ranges for the chain extender are from 0.01 to 5 percent, preferably 0.3 to 2.5 weight percent, based on the total
weight percent of the AAPE.
50 [0036] The preparation of polyesters and copolyesters is well known in the art (U.S. Pat. No 2,012,267, incorporated
herein by reference in its entirety.) Such reactions are usually carried out at temperatures from 150° C. to 300° C. in
the presence of polycondensation catalysts such as titanium tetrachloride, manganese diacetate, antimony oxide,
dibutyl tin diacetate, zinc chloride, or combinations thereof. The catalysts are typically employed in amounts between
10 to 1000 ppm, based on total weight of the reactants. For the purpose of the present invention, a representative
55 aliphatic polyester is the polycondensation product of dimethylglutarate and 1,6-hexanediol. This polyester, poly(hex-
amethylene glutarate), is produced when dimethylglutarate and 1,6-hexanediol are heated at approximately 210° C.
for 4 hours and then at 260° C. for 1.5 hours under vacuum in the presence of 100 ppm of Ti. A representative aliphatic-
aromatic copolyester is poly(tetramethylene glutarate-coterephthalate) containing 30 mole per cent terephthalate. This

6
 EP 1 254 766 A1

polyester is produced when dimethylglutarate, dimethyl terephthalate, and 1,4-butanediol are heated at 200° C. for 1
hour then at 245° C. for 0.9 hour under vacuum in the presence of 100 ppm of Ti present initially as Ti(OiPr)4.
[0037] In a second embodiment of the present invention, there is provided a multilayer film comprising:

5 (a) a first layer comprising

(i) from about 70 to 100 weight percent of at least one or more linear or branched or chain extended, random,
aliphatic-aromatic copolyester(s) having a MVTR value of at least 300 g-µm/m2-hour or g-mil/m2-day, as de-
termined in accordance with ASTM Test Method E-96D, and comprising repeating units of:
10

15

20

wherein

25 R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole
percent of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene
or oxylalkylene substituted with one to four substituents independently selected from the group consisting
of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C12 cycloalkylene (for example, 1,4-cyclohexanedimethanol);
30 C5-C12 cycloalkylene substituted with one to four substituents independently selected from the group con-
sisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene
or oxylalkylene substituted with one to four substituents independently selected from the group consisting
of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one
35 to four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4
alkoxy; and the mole percent of R2 is from about 35 to about 95;
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one
to four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4
alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently
40 selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is
from about 5 to about 65; and

(ii) from 0 to about 30 weight percent filler, and

45 (b) a second layer having in stretched form a MVTR value, according to ASTM E-96D, of at least about 500 g-µm/
m2-hour or g-mil/m2-day, and comprising

(i) from about 20 to about 65 weight percent of at least one or more thermoplastic polymer(s) selected from
the group consisting of a polyolefin and a linear or branched or chain extended, random, aliphatic-aromatic
50 copolyester of the first layer and
(ii) from about 35 to about 80 weight percent filler;

wherein the first layer is adjacent to the second layer and wherein the multilayer film, in stretched form, has a
MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM E-96D, of the at least
55 one or more linear or branched or chain extended, random, aliphatic-aromatic copolyester(s) of the first layer.

[0038] Preferably, the multilayer film in stretched form has a MVTR value greater than about 500 to about 10,000 g-
µm/m2-hour or g-mil/m2-day. Also, the second layer preferably has in stretched form a MVTR value, according to ASTM

7
 EP 1 254 766 A1

E-96D, of at least about 500 to about 10,000 g-µm/m2-hour or g-mil/m2-day.

[0039] In preparing the multilayer films of the invention where a polyolefin is utilized in the second layer, there may
be used any polyolefin that when filled with the appropriate type and amount of filler as described herein and, when
stretched, has a MVTR value, according to ASTM E-96D, of at least about 500 to about 10,000 g-µm/m2-hour or g-
5 mil/m2-day.
[0040] The polyolefins that may be used in the present invention are described as follows. The polyolefins can be
homopolymers of ethylene, propylene, copolymers thereof, or combinations thereof. Suitable polyolefins include high
density polyethylene, medium density polyethylene, linear low density polyethylene, or mixtures thereof. Polyolefin
copolymers are prepared with propylene or ethylene and at least one or more other olefin(s). Preferably, the olefins
10 are alpha-olefins. Typical density ranges for these linear low density polyethylenes are in the range of 0.90 to 0.94 g/
cc. Typical melt index ranges from 0.1 to 10 g/10 min (measured in accordance with ASTM D 1238-70). The olefins
may contain from about 2 to about 16 carbon atoms. The copolymer of ethylene or propylene and at least one other
olefin comprise an ethylene or propylene content of at least about 50 percent by weight of the total monomers involved.
Exemplary olefins that may be utilized herein are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene,
15 1-octene, 4-methylpent-1-ene, 1-decene, 1-dodecene, 1-hexadecene and the like. Also utilizable herein are polyenes
such as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4-vinylcyclohex-1-ene, 1,5-cyclooctadi-
ene, 5-vinylidene-2-norbornene and 5-vinyl-2-norbornene.
[0041] The ethylene homopolymer or interpolymer of the present composition may be prepared by any manner known
to those skilled in the art.
20 [0042] The filler useful in preparing the compositions of this invention in the first or second embodiments includes
any filler material that will result in a composition from which a stretched film that is produced is characterized by having
an increased MVTR as compared to a film prepared from the composition in the absence of filler. The amount of filler
utilized is any amount that is effective or sufficient to provide a composition from which there can be produced films
having the increased MVTR. The filler will be present in the polymer-filler composition in an amount of from 0 to about
25 80 percent by weight, preferably from about 20 to about 80 percent by weight, based on the total composition. However,
where a polyolefin is used in producing the composition, the filler will be present in an amount of from about 35 to about
80 percent by weight, based on the total composition.
[0043] Exemplary fillers that are suitable for use herein are inorganic fillers such as calcium carbonate, talc, clay,
kaolin, silica, diatomaceous earth, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, cal-
30 cium sulfate, aluminum hydroxide, zinc oxide, magnesium oxide, titanium oxide, aluminum oxide, mica, glass powder,
zeolite, silica clay, wood flour, cellulose, and the like. Preferred for use herein is a calcium carbonate, that may optionally
be coated with a fatty acid. A typical calcium carbonate is that supplied by English China Clay under the registered
trademark SUPERCOAT calcium carbonate, reported as being 97.6 weight percent calcium carbonate (prior to surface
treatment) with a mean particle size of 1 micron (top cut of 10 microns) and surface area of 7.2 m3/g (determined by
35 BET).
[0044] For many purposes, it may be desirable to incorporate other conventional additives with the polymeric com-
positions of the present invention. For example, there may be added antioxidants, heat and light stabilizers, dyes,
antistatic agents, lubricants, preservatives, processing aids, slip agents, antiblocking agents, pigments, flame retard-
ants, blowing agents, and the like. More than one additive may be used. The additive may be present in any desired
40 amount. Accordingly, the amount of additive utilized will depend upon the particular polymer and filler used and the
application or usage intended for the composition and film. Compositions containing such other additives are within
the scope of this invention. It is within the skill of the ordinary artisan in possession of the present disclosure to select
the appropriate additive(s) and amount thereof depending on the processing conditions and end use of the composition.
[0045] The polymer-filler compositions, and monolayer or multilayer films, can be prepared utilizing any means known
45 in the art, For example, filler containing compositions can be prepared in an apparatus such as a torque rheometer, a
single screw extruder or a twin-screw extruder. Formation of films can be achieved by melt extrusion, as described,
for example, in U.S. Patent No. 4,880,592, or by compression molding as described, for example, in U.S. Patent No.
4,427,614, or by any other suitable method.
[0046] The compositions may be fabricated into mono-layer or multi-layer films by any technique known in the art.
50 For example, mono-layer, or multilayer films may be produced by the well known cast film, blown film and extrusion
coating techniques, the latter including extrusion onto a substrate. Preferred substrates include woven and nonwoven
fabrics. Mono-layer, or multi-layer films produced by melt casting or blowing can be thermally bonded or sealed to a
substrate using an adhesive. The ordinary artisan, in possession of the present disclosure, can prepare such multi-
layer films and articles containing such films without undue experimentation.
55 [0047] The multilayer films of the present invention may be prepared by any method known in the art. For example,
the multilayer structures of this invention are readily prepared by conventional coextrusion processes, a conventional
in-line or off-line lamination process or a conventional extrusion coating process, all well known in the art. In general,
in a coextrusion process, the polymers are brought to the molten state and coextruded from a conventional extruder

8
 EP 1 254 766 A1

through a flat sheet die, the melt streams being combined in a coextrusion feed block or multimanifold die prior to
exiting the die. After leaving the die, the multi-layer film structure is quenched and removed for subsequent handling.
[0048] The monolayer or multilayer films described herein can be stretched by any known method. Stretching of a
film is defined herein as the elongation of a material beyond the yield point of the material to render permanent the
5 deformation of the material. In so doing, the films must be stretched at a temperature at least below the Vicat softening
point + 20°C, this temperature being determined by the exact stretching process used and the rate at which film is
being stretched (Vicat is determined by ASTM D1525). Typically stretching occurs at or below the Vicat softening point.
[0049] As shown hereinafter in the examples, cast multi-layer film was produced from the filler containing composi-
tions and unfilled polyester. ABA or AB type structures were prepared where (A) layers were filler containing polyester
10 and/or polyolefin compositions, and the (B) layer was unfilled and filled polyester. The multilayer films were prepared
by the following coextrusion process. Main extruder used was a conventional 5.08 cm diameter extruder, 30:1 L:D
(length:diameter) ratio, fitted with an internally cooled barrier screw with 3:1 compression ratio and twisted maddock
mixing section. Satellite extruders employed were 2.54 cm and 3.175 cm, 24:1 L:D, fitted with general purpose screws
with 3:1 compression ratios. A Precision Component feedblock (designed for 10/80/10 distribution) was used to convey
15 the melt to a conventional 76.2 cm coathanger die. A 2-roll cast film downstack configuration was used for quenching
the melt. Additionally mono-layer film was produced from the filler containing polyester by introducing the filler-con-
taining polyester composition into the feed hoppers of a 3.81 cm, 24:1 Killian single screw extruder equipped with a
30.48 cm wide film die and a chilled casting roll. The extrusion conditions used to produce the films were as follows:

20 Barrel Temperatures
Zone 1 °C 150
Zone 2 °C 150
Zone 3 °C 150
25
Clamp °C 150
Adaptor °C 150
Die Temperatures
30
Zone 1 °C 150
Zone 2 °C 150
Zone 3 °C 150

35
[0050] The monolayer or multilayer films described herein can be stretched by any known method. Stretching of a
film is defined herein as the elongation of a material beyond the yield point of the material to render permanent the
deformation of the material. In so doing, the films must be stretched at a temperature at least below the Vicat softening
point + 20°C, this temperature being determined by the exact stretching process used and the rate at which film is
being stretched (Vicat is determined by ASTM D1525). Typically stretching occurs at or below the Vicat softening point.
40
[0051] Such known methods of stretching are roll-to-roll, tenter frame, ringroll or intermeshing, TM Long, and hand
stretching. The multi-layer and mono-layer films of the present invention were stretched via hand stretching at room
temperature and accordingly were fabricated at a thickness of about 75 to about 125 µm.
[0052] Roll-to-roll stretching is generally performed by passing a film across a series of rolls where adjacent, down-
stream rolls are rotating at higher rates than upstream rolls. The simplest example is a film passing over two rolls, the
45
second rotating faster than the first resulting in the film being stretched in the region in between the two rolls. Tenter
frame stretching involves gripping a film and then moving the grips apart from one another, stretching the film in be-
tween. Such processes can involve preheating of the film prior to stretching and heat setting after stretch.
[0053] Ring-roll stretching or intermesh stretching is performed by passing the film between two parallel rolls having
a surface of intermeshing gear-like teeth where the degree of stretch that is applied to the film is controlled by the
50
degree of gear engagement, i.e., how close the rolls are brought together. Machine direction stretching is accomplished
using rolls where the gear-like teeth span the cross direction of the upper and lower roll analogous to a wide cog or
pitch spur gears. Cross direction stretching is accomplished by covering the surface of the rolls with intermeshing disks.
Passing a film through the machine direction stretching device produces uniform stretched bands spanning the cross
direction of the film. Passing a film through the cross direction stretching device produces uniform stretched bands
55
spanning the machine direction of the film. Passing film through both of these devices produces a film bearing a cross-
hatched or checkered pattern.
[0054] The TM Long film stretcher (named for the producer) uniaxially or biaxially stretches samples of pressed,

9
 EP 1 254 766 A1

blown, or extruded film. The operation of the film stretcher is based upon the movement of two drawbars at right angles
to each other upon hydraulically driven rods. There is a fixed draw bar opposed to each moving draw bar. These pairs
of opposed moving and fixed draw bars, to which the four edges of the film specimen are attached, form the two axes
at right angles to each other along which the specimen is stretched in any stretch ratio up to four or seven times original
5 size, depending on the machine being used. Samples are placed in grips on the machine and heated prior to stretching
if desired. The outputs from the device are stress versus elongation data (if desired) at the temperature of the experiment
and the stretched film.
[0055] Hand stretching is performed by gripping a piece of film between one's hands and then moving the hands
away from each other allowing the film to stretch in between. The film is stretched to produce a piece of whitened film
10 at least three inches long. Films can be hand stretched in one direction (uniaxial) and then gripped again in the cross
direction to stretch again from 0.5 to 500 percent elongation and create biaxial orientation.
[0056] For Examples 1-8 samples were uniaxially stretched by the hand method and then biaxially stretched samples
were prepared by gripping the uniaxially stretched film in the cross direction and stretching from 10 to 30 percent
elongation.
15 [0057] Additionally, the present invention is directed to articles of manufacture incorporating the novel multi-layer
films, of the present invention. Such articles include, but are not limited to, garments, diapers sanitary napkins, medical
protective garments, surgical incise drapes, transdermal patches, wound care bandages and dressings, intravenous
site dressings, and ostomy site dressings, house wrap, and others. The articles can be produced utilizing any suitable
technique.
20 [0058] The invention will be more readily understood by reference to the following examples. There are, of course,
many other forms of this invention which will become obvious to one skilled in the art, once the invention has been
fully disclosed, and it will accordingly be recognized that these examples are given for the purpose of illustration only,
and are not to be construed as limiting the scope of this invention in any way.

25 EXAMPLES

[0059] In the following examples the test procedures listed below were used in evaluating the properties of the pol-
ymer component, and the physical properties of the multi-layer films produced.

30 (a) Moisture Vapor Transmission Rate (MVTR) is measured according to ASTM Test Method E-96D. The apparatus
for this experiment consists of a test dish, environmental Thermotron test chamber, and a balance. The test dish
is noncorroding and is impermeable to liquid water and water vapor. The mouth area of the dish defines the test
area such that the overlay material is masked to eliminate this potential source of error. The water level is filled to
1.91 cm below the mouth to avoid contact of water with the specimen and covers the dish bottom throughout the
35 entire experiment. The Thermotron test chamber Model SM5.5S controls the temperature and relative humidity.
The temperature for this work was selected at 32°C (90°F), which is the standard test condition designated as
ASTM E-96D. The relative humidity is maintained at 50 ± 2%. Air is continuously circulated over the face of the
film at a rate of 200 m/s (meters per second). The Mettler P1200 balance detects changes in weight smaller than
1% (0.01 grams) of the weight change during the steady state period. Samples are secured on the test dish and
40 weighed. The samples are then placed into the test chamber for two hours and then weighed again. The samples
are put back into the oven for a total of 24 hours and the weights are measured twice more over the 24-hour period.
The MVTR of each samples is calculated by the following equation:

45
MVTR=(g*L)/(A)(T)

Where

g= weight change during test (grams)

50 A= test area (m2)
T= time = hours (day)
L= film thickness µm (mil)

[0060] The weight loss data is plotted and the slope of the straight line is the rate of the water vapor transmission
55 through the film. The slope of the line is then divided by the area of the sample tested and multiplied by the film thickness
to obtain a normalized MVTR.

10
 EP 1 254 766 A1

Examples 1-2

[0061] In Examples 1 and 2 multi-layer structures were prepared having three layers where the outer layers were
comprised of a filled polyethylene and the center layer was either unfilled AAPE (Example 1) or AAPE containing 20
5 weight percent (wt%) filler (Example 2).
[0062] In producing the filled polyethylene layer, the polyethylene component and the filler were compounded in a
Kobelco continuous mixer model NEX-T60. The mixer was operated at 205 °C and at a mixing speed of 800 rpm. The
polyethylene component and the filler were fed to the mixer to produce a polyethylene filler composition containing 50
wt% filler. Additionally, 100 ppm Dynamar FX 9613 processing aid (supplied by Dyneon, Oakdale, MN) and 150 ppm
10 Irganox B215 antioxidant (supplied by Ciba Specialty Chemicals Corporation, Tarrytown, NY) were added to the pol-
yethylene filler composition during mixing. The filler utilized to prepare the polyethylene compositions was Filmlink™
400 calcium carbonate. The polyethylene of Examples 1 and 2 was an ethylene-1-hexene interpolymer having a density
of 0.915 g/cc, and a melt index of 3 g/10 min.
[0063] The AAPE component was poly(tetramethylene adipate-co-terephthalate), a copolyester of butane diol with
15 adipic acid and terephthalic acid where the adipic to terephthalic acid ratio is 57/43. In preparing the AAPE compositions
containing 20 wt% filler in the examples herein, the AAPE component and the filler were compounded in a Kobelco
continuous mixer model NEX-T60. The mixer was operated at 175 °C and at a mixing speed of 600 rpm. The AAPE
component and the filler were fed to the mixer to produce an AAPE filler composition containing 70 wt% filler. This
AAPE filler composition was then pellet-pellet blended with unfilled AAPE to reduce the filler content to 20 wt%. The
20 filler utilized was Filmlink™ 500 calcium carbonate. Each of the compositions of Examples 1 and 2 were coextruded
into multi-layer film as shown herein. The AAPE components were dried overnight to remove moisture prior to coex-
trusion. Each of the films of Examples 1 and 2 were then biaxially stretched at room temperature, as shown herein, by
means of the hand stretching method. The stretched films of Examples 1 and 2 were then evaluated to determine the
properties set forth in Table 1. Also shown in Table 1 is the MVTR of a stretched mono-layer of the same polyethylene
25 filler component stretched at room temperature uniaxially by the hand stretching method. The AAPE used for these
examples has a reported MVTR of 534 g-µm/m2/hour or g-mil/m2-day as shown herein.

Table 1
Film Properties
30
Example No. 1 2 Polyethylene -filler monolayer Unstretc hed Unfilled AAPE
Average MVTR, g-µm/m2/hour 767 914 926 534
Stretched film thickness (µm) 25.8 32.3 16.5 ---
35 Unstretched film layer thickness
Top layer (µm) 54 35 54 38.5
Center layer (µm) 21 21.3 --- ---
Bottom layer (µm) 19 25 --- ---

40
[0064] From Examples 1 and 2, it is observed that the multilayer films of the present invention are characterized by
having increased MVTR values, as compared to the MVTR value of the control film, comprising unfilled AAPE. The
observed MVTR values of the multilayer films of the present invention are indicative of films possessing breathability
characteristics. In addition, it is expected that the multilayer films of the present invention will be a barrier to virus,
bacteria, and/or wind.
45

Examples 3-8

[0065] In Examples 3-6, multi-layer films were prepared having three layers where the outer layers were comprised
of 50 wt% filled AAPE and the center layer was either unfilled AAPE (as in Examples 3, 4, and 7) or AAPE containing
50
20 wt% filler (as in Examples 5 and 6). Example 7 is a two layer film comprised of a first layer of 50 wt% filled AAPE
and a second layer of unfilled AAPE. Example 8 is a single layer film comprised of 50 wt% filled AAPE. The AAPE
component was poly(tetramethylene adipate-co-terephthalate), a copolyester of butane diol with adipic acid and tereph-
thalic acid where the adipic to terephthalic acid ratio is 57/43. In preparing the AAPE compositions containing 50 and
20 wt% filler of the examples herein, the AAPE component and the filler were compounded in a Kobelco continuous
55
mixer model NEX-T60. The mixer was operated at 175°C, and a mixing speed of 600 rpm. The AAPE component and
the filler were fed to the mixer to produce an AAPE filler composition containing 70 wt% filler. This AAPE filler compo-
sition was then pellet-pellet blended with unfilled AAPE to reduce the filler content to 50 or 20 wt%. The filler utilized

11
 EP 1 254 766 A1

was Filmlink™ 500 calcium carbonate. Each of the compositions of Examples 3-7 were coextruded into multi-layer film
as shown herein. Example 8 was extruded into monolayer film as shown herein. The components were dried overnight
to remove moisture prior to coextrusion. Each of the films of Examples 3-8 were then biaxially stretched at room tem-
perature, as shown herein, by means of the hand stretching method. The stretched films of Examples 3-8 were then
5 evaluated to determine the properties set forth in Table 2. The MVTR of a monolayer film of the same unfilled AAPE
component is shown in Table 1.

Table 2
Film Properties
10
Example No. 3 4 5 6 7 8
Average MVTR, g-µm/m2/hour 1190 1074 966 1462 1665 1931
Stretched film thickness (µm) 30 45 27.8 39 39.3 28.5
15 Unstretched film layer thickness
Top layer (µm) 50 51.5 31 52 46 -
Center layer (µm) 32 33 36 37 -
Bottom layer (µm 19 50 36 30 15.8 -

20
[0066] From the data in Examples 3-7, it is observed that the multilayer films of the present invention are characterized
by having MVTR values increased when compared with the MVTR value of a film formed from a mono-layer of unfilled
AAPE. As in Examples 1 and 2, the multilayer films of Examples 3-7, have MVTR values that are indicative of films
having good breathability characteristics. In addition, it is expected that the multilayer films of the present invention
will be a barrier to virus, bacteria and/or wind.
25
[0067] Examples 1-7 have MVTR values comparable to the filled and stretched monolayer films shown in Tables 1
and 2. However, filled and stretched monolayer films are not expected to be a barrier to virus, bacteria and/or wind.

Examples 9-12
30
[0068] As shown hereinafter in Examples 9-12, the multi-layer film was produced from the filler containing AAPE
polyester and either unfilled polycaprolactone (PCL) polyester (Examples 9, 10), or unfilled polyester-ether (Example
11), or unfilled polyurethane (Example 12). ABA type structures were prepared where (A) layers were filler containing
AAPE polyester, and the (B) layer was either unfilled PCL polyester (Examples 9, 10), or unfilled polyester-ether (Ex-
ample 11), or unfilled polyurethane (Example 12).
35
[0069] The multilayer films were prepared by the following coextrusion process. To feed the filler containing polyester,
the main extruder used was a conventional 2.54 cm diameter Killian extruder, 24:1 L:D (length:diameter) ratio, fitted
with a feed screw with 3:1 compression ratio and twisted maddock mixing section. A second identical extruder was
employed to feed the unfilled materials. A Killian coextrusion feedblock was used to convey the melt to a conventional
15.24 cm coathanger die. A 2-roll cast film downstack configuration was used for quenching the melt. Additionally
40
mono-layer film was produced from the unfilled polymers by introducing the unfilled polymers into the feed hoppers of
a 24:1 Killian single screw extruder equipped with a film die and a chilled casting roll. The extrusion conditions used
to produce the films were as follows:

45
Examples 9-10 Example 11 Example 12
Barrel Extruder Extruder Extruder
Temperature Main 2nd Main 2nd Main 2nd
Zone 1 °C 230 71 200 200 200 215
50
Zone 2 °C 230 340 230 230 230 220
Zone 3 °C 230 340 230 230 230 220
Die Temperature

55 Zone 1 °C 230 390 230 230 230 220

Zone 2 °C 230 230 230 230 230 220

12
 EP 1 254 766 A1

[0070] In Examples 9-10, multi-layer films were prepared having three layers where the outer layers were comprised
of 50 wt% filled AAPE and the center layer was unfilled polycaprolactone, PCL, (CAPA 6500 from Solvay). The AAPE
component was poly(tetramethylene adipate-co-terephthalate), a copolyester of butane diol with adipic acid and tereph-
thalic acid where the adipic to terephthalic acid ratio is 57/43. In preparing the AAPE compositions containing 50 wt%
5 filler of the examples herein, the AAPE component and the filler were compounded in a Kobelco continuous mixer
model NEX-T60. The mixer was operated at 176 °C, and a mixing speed of 600 rpm. The AAPE component and the
filler were fed to the mixer to produce an AAPE filler composition containing 70 wt% filler. This AAPE filler composition
was then pellet-pellet blended with unfilled AAPE to reduce the filler content to 50 or 20 wt%. The filler utilized was
Filmlink™ 500 calcium carbonate. Each of the compositions of Examples 9-10 were coextruded into multi-layer film
10 as shown herein. The components were dried overnight to remove moisture prior to coextrusion. Each of the films of
Examples 9-10 were then biaxially stretched at room temperature, as shown herein, by means of the hand stretching
method. The stretched films of Examples 9-10 were then evaluated to determine the properties set forth in Table 3.
The MVTR of a monolayer film of the same unfilled AAPE component is shown in Table 1 and the same unfilled PCL
component with a film thickness of 169 µm is shown in Table 3.
15
Table 3
Film Properties
Example No. 9 10 Unfilled PCL
20 Average MVTR, g-µm/m2/hour 2036 2033 393
Stretched film thickness (µm) 60.3 59 -
Unstretched film layer thickness
Top layer (µm) 68 81.5 -
25 Center layer (µm) 24 30.5 -
Bottom layer (µm 54.5 68.5 -

[0071] In Example 11, multi-layer films were prepared having three layers where the outer layers were comprised of
50 wt% filled AAPE and the center layer was unfilled polyester-ether, (Hytrel from DuPont, a copolyester block copol-
30
ymer of poly(butylene terephthalate) and poly(tetramethylene glycol)). The AAPE component was poly(tetramethylene
adipate-co-terephthalate), a copolyester of butane diol with adipic acid and terephthalic acid where the adipic to tereph-
thalic acid ratio is 57/43. In preparing the AAPE compositions containing 50 wt% filler of the examples herein, the
AAPE component and the filler were compounded in a Kobelco continuous mixer model NEX-T60. The mixer was
operated at 175 °C, and a mixing speed of 600 rpm. The AAPE component and the filler were fed to the mixer to
35
produce an AAPE filler composition containing 50 wt% filler. The filler utilized was Omtacarb™ 2 SS T-FL calcium
carbonate. The compositions of Example 11 was coextruded into multi-layer film as shown herein. The components
were dried overnight to remove moisture'prior to coextrusion. The films of Examples 11 was then biaxially stretched at
room temperature, as shown herein, by means of the hand stretching method. The stretched film of Example 11 was
then evaluated to determine the properties set forth in Table 4. The MVTR of a monolayer film of the same unfilled
40
AAPE component is shown in Table 1 and the same unfilled polyester-ether component with a film thickness of 75.5
µm is shown in Table 4.

Table 4

45 Film Properties
Example No. 11 Unfilled Polyester-ether
Average MVTR, g-µm/m2/hour 1688 699
Stretched film thickness (µm) 56.8 -
50
Unstretched film layer thickness
Top layer (µm) 51 -
Center layer (µm) 43.3 -
Bottom layer (µm 42 -
55
[0072] In Example 12, multi-layer films were prepared having three layers where the outer layers were comprised
of 50 wt% filled AAPE and the center layer was unfilled polyurethane, (ESTANE 58149 from BF Goodrich). The AAPE
component was poly(tetramethylene adipate-co-terephthalate), a copolyester of butane diol with adipic acid and tereph-

13
 EP 1 254 766 A1

thalic acid where the adipic to terephthalic acid ratio is 57/43. In preparing the AAPE compositions containing 50 wt%
filler of the examples herein, the AAPE component and the filler were compounded in a Kobelco continuous mixer
model NEX-T60. The mixer was operated at 175 °C, and a mixing speed of 600 rpm. The AAPE component and the
filler were fed to the mixer to produce an AAPE filler composition containing 50 wt% filler. The filler utilized was Omt-
5 acarb™ 2 SS T-FL calcium carbonate. The composition of Example 12 was coextruded into multi-layer film as shown
herein. The components were dried overnight to remove moisture prior to coextrusion. The film of Examples 12 was
then biaxially stretched at room temperature, as shown herein, by means of the hand stretching method. The stretched
film of Example 12 was then evaluated to determine the properties set forth in Table 5. The MVTR of a monolayer film
of the same unfilled AAPE component is shown in Table 1 and the same unfilled polyester-ether component with a film
10 thickness of 96.3 mil is shown in Table 5.

Table 5
Film Properties

15 Example No. 12 Unfilled Polyurethane

Average MVTR, g-mil/m2/day 1919 488
Stretched film thickness (µm) 52 -
Unstretched film layer thickness
20 Top layer (µm) 55 -
Center layer (µm) 8.5 -
Bottom layer (µm) 26 -

[0073] The invention has been described above in detail with particular reference to preferred embodiments thereof,
25
but it will be understood that variations and modifications other than as specifically described herein can be effected
within the spirit and scope of the invention. Moreover, all patents, patent applications, provisional patent applications,
and literature references cited above are incorporated herein by reference for any disclosure pertinent to the practice
of this invention.
30

Claims

1. A multilayer film comprising:

35
(a) a first layer comprising from about 70 to 100 weight percent of at least one or more thermoplastic polymer
(s) having a MVTR value of at least 300 g-µm/m2-hour or g-mil/m2-day, as determined in accordance with
ASTM Test Method E-96D, and from 0 to about 30 weight percent filler, and
(b) a second layer comprising from about 20 to about 80 weight percent of at least one or more thermoplastic
polymer(s) and from about 20 to about 80 weight percent filler, the second layer having in stretched form a
40
MVTR value, according to ASTM E-96D, greater than the MVTR value, according to ASTM E-96D, of the at
least one or more thermoplastic polymer(s) of the second layer;

wherein the second layer comprises an amount of filler differing from the amount of filler in the first layer when the
at least one or more thermoplastic polymer(s) of the first layer and the at least one or more thermoplastic polymer
45
(s) of the second layer are the same,
wherein the first layer is adjacent to the second layer, and
wherein the multilayer film, in stretched form, has a MVTR value, according to ASTM E-96D, greater than the
MVTR value, according to ASTM E-96D, of the at least one or more thermoplastic polymer(s) of the first layer.
50
2. The multilayer film according to Claim 1 wherein the at least one or more thermoplastic polymer(s) of the first layer
and the at least one or more thermoplastic polymer(s) of the second layer are the same.

3. The multilayer film according to Claim 1 wherein the at least one or more thermoplastic polymer(s) of the first layer
has a MVTR value ranging from at least 300 to about 10,000 g-µm/m2-hour or g-mil/m2-day.
55

4. The multilayer film according to Claim 1 wherein the thermoplastic polymer of the first layer is selected from the
group consisting of polylactic acid polymers and copolymers, polyurethanes, polyhydroxybutyrate copolymers with

14
 EP 1 254 766 A1

co-monomers of valeric acid and gaµma hydroxy alkanoates, polyesteramides, poly vinyl alcohol, cellulose esters,
polycaproyl lactone polymers and copolymers, copolymers of terephthalic acid, and isophthalic acid, with diols
and polytetramethylene glycol or polypropylene glycol, polyether amides with polyethylene glycol, polyethylene
glycol modified polybutylene terephthalate, polyether urethanes, and a linear or branched or chain extended, ran-
5 dom, aliphatic-aromatic copolyester comprised of repeat units of:

10

15

wherein

20 R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole
percent of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene or
oxylalkylene substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four sub-
25 stituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene
or oxylalkylene substituted with one to four substituents independently selected from the group consisting of
halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four
30 substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R2 is from about 35 to about 95;
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one to
four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy;
C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently selected
35 from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is from about 5
to about 65;
or blends thereof.

5. The multilayer film according to Claim 1, wherein the thermoplastic polymer of the first layer is a linear or branched
40 or chain extended, random, aliphatic-aromatic copolyester comprised of repeat units of:

45

50

wherein

55 R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole
percent of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene or
oxylalkylene substituted with one to four substituents independently selected from the group consisting of halo,

15
 EP 1 254 766 A1

C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four sub-
stituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene
5 or oxylalkylene substituted with one to four substituents independently selected from the group consisting of
halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four
substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R2 is from about 35 to about 95;
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one to
10 four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy;
C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently selected
from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is from about 5
to about 65;

15 6. The multilayer film according to Claim 5 wherein R1 is selected from C2-C8 alklyene and is present in an amount
of from about 90 to 100 mole percent, R3 is present in an amount of from 0 to about 10 mole percent; R2 is selected
from one or more of the groups consisting of C2-C8 alkylene or oxyalkylene and is present in an amount of from
about 35 to about 95 mol percent; and R4 is selected from one or more of the groups consisting of C6-C10 aryl and
is present in an amount of from about 5 to about 65 mole percent.
20
7. The multilayer film according to Claim 5 wherein R1 is selected from C2-C4 alklyene and is present in an amount
of from about 95 to 100 mole percent; R3 is present in an amount of from 0 to about 5 mole percent; R2 is selected
from one or more of the groups consisting of C2-C6 alkylene or C2 oxyalkylene and is present in an amount of from
about 35 to about 65 mole percent; and R4 is a 1,4-disubstituted-C6 aryl and is present in an amount of from about
25 35 to about 65 mole percent.

8. The multilayer film according to Claim 5 wherein the at least one or more linear or branched or chain extended,
random, aliphatic-aromatic copolyester(s) is based on 100 mole percent of an acid component and 100 mole
percent of a diol component and is selected from the group consisting of copolyesters comprising:
30
(a) an acid component of from about 30 to about 75 mole percent glutaric acid and from about 25 to about 70
mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol;
(b) an acid component of from about 30 to about 95 mole percent succinic acid and from about 5 to about 70
35 mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol; and
(c) an acid component of from about 30 to about 75 mole percent adipic acid and from about 25 to about 70
mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol.
40
9. The multilayer film according to Claim 8 wherein the modifying diol is selected from the group consisting of 1,4-cy-
clohexanedimethanol, triethylene glycol, polyethylene glycol and neopentyl glycol.

10. The multilayer film according to Claim 8 wherein the acid component comprises about 50 to about 60 mole percent
45 adipic acid and about 40 to about 50 mole percent terephthalic acid and the glycol component comprises at least
about 95 to 100 mole percent 1,4-butanediol.

11. The multilayer film according to Claim 10 wherein the acid component comprises from about 55 to about 60 mole
percent adipic acid and about 40 to about 45 mole percent terephthalic acid.
50
12. The multilayer film according to Claim 1, in stretched form.

13. An article of manufacture comprising the multilayer film according to

55 Claim 1.

14. The multilayer film according to Claim 1 wherein the filler is calcium carbonate.

16
 EP 1 254 766 A1

15. A multilayer film comprising:

(a) a first layer comprising

5 (i) from about 70 to 100 weight percent of at least one or more linear or branched or chain extended,
random, aliphatic-aromatic copolyester(s) having a MVTR value of at least 300 g-µm/m2-hour or g-mil/
m2-day, as determined in accordance with ASTM Test Method E-96D, and comprising repeat units of:

10

15

20
wherein

R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the
mole percent of R1 is from about 80 to 100;
25 R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8
alkylene or oxylalkylene substituted with one to four substituents independently selected from the
group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene
substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R3 is from 0 to about 20;
30 R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12
alkylene or oxylalkylene substituted with one to four substituents independently selected from the
group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene
substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R2 is from about 35 to about 95;
35 R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with
one to four substituents independently selected from the group consisting of halo, C6-C10 aryl, and
C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents
independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole
percent of R4 is from about 5 to about 65; and
40
(ii) from 0 to about 30 weight percent filler, and

(b) a second layer having in stretched form a MVTR value, according to ASTM E-96D, of at least about 500
g-µm/m2-hour or g-mil/m2-day and comprising
45
(i) from about 20 to about 65 weight percent of at least one or more thermoplastic polymer(s) selected
from the group consisting of a polyolefin and a linear or branched or chain extended, random, aliphatic-
aromatic copolyester of the first layer and
(ii) from about 35 to about 80 weight percent filler;
50
wherein the first layer is adjacent to the second layer and
wherein the multilayer film, in stretched form, has a MVTR value, according to ASTM E-96D, greater than the
MVTR value, according to ASTM E-96D, of the at least one or more linear or branched or chain extended,
random, aliphatic-aromatic copolyester(s) of the first layer.
55
16. The multilayer film according to Claim 15 wherein the at least one or more linear or branched or chain extended,
random, copolyester(s) of the first layer has a MVTR value ranging from at least 300 to about 3000 g-µm/m2-hour
or g-mil/m2-day.

17
 EP 1 254 766 A1

17. The multilayer film according to Claim 15 wherein the thermoplastic polymer of the second layer is a linear or
branched or chain extended, random, aliphatic-aromatic copolyester comprised of repeating units of:

10

15 wherein

R1 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene and the mole
percent of R1 is from about 80 to 100;
R3 is selected from one or more of the groups consisting of C2-C8 alkylene or oxylalkylene; C2-C8 alkylene or
20 oxylalkylene substituted with one to four substituents independently selected from the group consisting of halo,
C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four sub-
stituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R3 is from 0 to about 20;
R2 is selected from one or more of the groups consisting of C2-C12 alkylene or oxyalkylene; C2-C12 alkylene
25 or oxylalkylene substituted with one to four substituents independently selected from the group consisting of
halo, C6-C10 aryl, and C1-C4 alkoxy; C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four
substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the
mole percent of R2 is from about 35 to about 95; and
R4 is selected from one or more of the groups consisting of C6-C10 aryl; C6-C10 aryl substituted with one to
30 four substituents independently selected from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy;
C5-C10 cycloalkylene; C5-C10 cycloalkylene substituted with one to four substituents independently selected
from the group consisting of halo, C6-C10 aryl, and C1-C4 alkoxy; and the mole percent of R4 is from about 5
to about 65.

35 18. The multilayer film according to Claim 15 wherein the second layer in stretched form has a MVTR value ranging
from at least about 500 to about 10,000 g-µm/m2-hour or g-mil/m2-day.

19. The multilayer film according to Claim 15 wherein the filler is calcium carbonate.

40 20. The multilayer film according to Claim 15 wherein R1 is selected from C2-C8 alklyene and is present in an amount
of from about 90 to 100 mole percent, R3 is present in an amount of from 0 to about 10 mole percent; R2 is selected
from one or more of the groups consisting of C2-C8 alkylene or oxyalkylene and is present in an amount of from
about 35 to about 95 mol percent; and R4 is selected from one or more of the groups consisting of C6-C10 aryl and
is present in an amount of from about 5 to about 65 mole percent.
45
21. The multilayer film according to Claim 15 wherein R1 is selected from C2-C4 alklyene and is present in an amount
of from about 95 to 100 mole percent; R3 is present in an amount of from 0 to about 5 mole percent; R2 is selected
from one or more of the groups consisting of C2-C6 alkylene or C2 oxyalkylene and is present in an amount of from
about 65 to about 35 mole percent; and R4 is a 1,4-disubstituted-C6 aryl and is present in an amount of from about
50 35 to about 65 mole percent.

22. The multilayer film according to Claim 15 wherein the at least one or more linear or branched or chain extended,
random, aliphatic-aromatic copolyester(s) is based on 100 mole percent of an acid component and 100 mole
percent of a diol component and is selected from the group consisting of copolyesters comprising:
55
(a) an acid component of from about 30 to about 75 mole percent glutaric acid and from about 25 to about 70
mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol;

18
 EP 1 254 766 A1

(b) an acid component of from about 30 to about 95 mole percent succinic acid and from about 5 to about 70
mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol; and
(c) an acid component of from about 30 to about 75 mole percent adipic acid and from about 25 to about 70
5 mole percent terephthalic acid and a diol component of from about 90 to 100 mole percent 1,4-butanediol and
from 0 to about 10 mole percent of a modifying diol.

23. The multilayer film according to Claim 22 wherein the modifying diol is selected from the group consisting of 1,4-cy-
clohexanedimethanol, triethylene glycol, polyethylene glycol and neopentyl glycol.
10
24. The multilayer film according to Claim 22 wherein the acid component comprises from about 50 to about 60 mole
percent adipic acid and about 40 to about 50 mole percent terephthalic acid and the glycol component comprises
at least about 95 to 100 mole percent 1,4-butanediol.

15 25. The multilayer film according to Claim 24 wherein the acid component comprises from about 55 to about 60 mole
percent adipic acid and about 40 to about 45 mole percent terephthalic acid.

26. The multilayer film according to Claim 15, in stretched form.

20 27. The multilayer film according to Claim 26 wherein the multilayer film has a MVTR value greater than about 500 to
about 10,000 g-µm/m2-hour or g-mil/m2-day.

28. The multilayer film according to claim 17, in stretched form.

25 29. An article of manufacture comprising the multilayer film according to Claim 15.

30. An article of manufacture comprising the multilayer film according to Claim 17.

31. An article of manufacture comprising the multilayer film according to Claim 28.
30
32. An article of manufacture comprising the multilayer film according to Claim 12.

35

40

45

50

55

19
EP 1 254 766 A1

20
EP 1 254 766 A1

21