CA1191439A

CA1191439A - Flexible layered product

Info

Publication number: CA1191439A
Application number: CA000441606A
Authority: CA
Inventors: Cornelius M.F. Vrouenraets; Doetze J. Sikkema
Original assignee: Akzo NV
Current assignee: Akzo NV
Priority date: 1982-12-02
Filing date: 1983-11-21
Publication date: 1985-08-06
Also published as: JPS59111847A; ATE27471T1; DE3371803D1; EP0111360A1; US4493870B1; DE8334353U1; EP0111360B2; EP0111360B1; JPH0148872B2; US4493870A

Abstract

A B S T R A C T

Flexible layered product for use in waterproof garments or tents of a textile material covered with a waterproof material having a water vapour transmission rate of at least 1000 g/m2 day, the textile material being covered with a film of a copolyether ester consisting of a plurality of recurrent intralinear long-chain ester units and short-chain ester units which are randomly joined head-to-tail through ester bonds, said long-chain ester units corresponding to the formula:

and said short-chain ester units corresponding to the formula:

Description

~le~ible layered prod~lot The inventlon relates to a 1exible layered product suitable for the manufacture therefrom of waterproof gannen~s or tents of a textile mate-rial covered with a waterproof material having a water vapour transmis-sion rate o~ at lea~t 1000 g/m day.
Plexible layered product6 of the type indicated above are disclo~ed in~ritish Patent Application 2 024 100.
~he products descrlbed in it, which ~re to be used Eor the ~anufactt~re therefro~ of, or instance, rainwea~, ar~ fo-med of a te~tile material which i8 succe~sively covered with a microporous layer of ~ for instance, expanded porous PTFE and a hydrophilic layer of, for lnstance, a poly-etherpol.yurethane which permit~ the transfer through it of water vapour but preventa the passage of surface tension lowering agents æuch as those contained in perspiration, etc.
~or use in garments and the like the textile material may optionally ~till be rendered hydrophobic.
Although these known products constitute a remarkable advance in the development ~f waterpro~f, breathable rainwear, they stlll display seve-ral disadvantages~ The price of the porous material is relatively high, partlcularly if ~se i8 made of porous PTFB film. Moreover, the layers of the hydrophilic material6 are relatively thick, which generally has a detrimental effect on the suppleness of th~ product.
Special pre~erence, however, is given to the use Df porous PTFE film both because of the strongly hydrophobic character o~ PTFE and the possibility of making a porous structure having pores measuring less than about 0,2 ~m in diameter. This film has the special advantage that although its porosity permits the passage of water vapour~ it is water-proof under a hydrostatic head of 25 cm water, which is determined wlth a modified Sutter's test apparatus, as described in the afore-mentioned 30 British Patent Specification 2 024 100~
In all the examples of said patent specification these porous fil~s are covered with relatively thick layers of highly hydrophilic materials7 which may lead to a high degree of wat~r absorption and, hence, strong swelling.

3 ~
:2 ~ AKU l~g3 ~

U~e oE very much thinner layers of thes0 ~aterials, for instance in the order o lO to 20 ~, may readily lead to ~echanical da~age in the wet ~t~

The present invention provldes flexible layered products which do not display the afore-mentioned disadvantage~ or only to a ~ar ~aller extent.
The invention COn8iBtS in that with the flexible layered products of the type mentioned in the opening paragrclph the textile material is covered with ~ ~ilm of a copol~ether ester consisting of a plurality of recurrent intralinear long-chain es~er units and short-chain ester units which are randomly joined head-to-tail through ester bonds, said long-cbain ester units corresponding to the for~ula:
O
~ n ---O - G ~ O ~ C ~ R ~ C ~
and said short-chain ester units corresponding to the fon~ula:

~ O - D - O - C - R - C -~
where G is a divalent radical re~in;ng after removal of terMinal hy-droxyl groups from at le~st one long-chain glycol having a molecular weight in the range of 800 to 6QOO and an atomic ratio of carbo~ to oxygen in the range of ~,0 to 4,3, at least 70~ by weight of the long-chain glycol having a carbon to oxygen r~tio in the range of 2,0 to 2,4,R is a divalent radical rem~inin9 after removal of carboxyl groups from at least one carboxylic acid having a ~olecular weight less than 300, and D is a divalent radical re~ ing after removal of hydroxyl groups fro~ a~ leas~ one diol having a molecular weight less than ~50, at least ~0 mole ~ of the dicarboxylic acid used consisting of terephthalio acid or the ester forming equlvalents thereof and at least 80 mole ~ of the lo~ molecular weight diol consisting of 1, 4-butanediol or the ester forming equivalents thereof~ the sum of the mole percentages of the dicarboxylic acid which is not terephthalic acid or the ester forming equivalents thereof and of the -low molecular weight diol which is not l/4-butanediol ~r the ester forming equivalents thereof is not higher than 20 and the ~hort-chain ester units for~ 50-754 b~ ~eight of the copolyether ester.

-- ~KU l893 B

It should be added that ln the U.S. Patent Specificatlon 3 0~3 192 the use i~ recommended of copolyether ester film of polyetbylene terephtha-late modlfied ~ith abGut 35 to 75~ by weight of polyethylene oxide gly-col for the manufacture therefrom of shoe-upper leather. For the manu-facture of rainwear~ however, the polymer~ mentioned in it have not beenfound quite suitable in tbat they are not onl~ less permeable to water vapour, but absorb ar more water than desirable for said use~

Suitable te~tile materials are those that are as a rule employed for the manufacture o~ rainwear, sleepin~ bags, tents and the like. Speclal 10 mention is made here o fabrics based on polyethylene terephthalate and polyamide 6 or 66. The most Eavourable results are obtained generally when the textlle material is rendered hydrophobic. This is preferably done after lamination with the copolyether ester film~
When the hydrophobic material i~ wetted for instance by rain, the water 15 will j~st run ofP it in the form of drops.

The de~ree of water vapo~r permeability of the copolyether ester fllm is, of course~ not ohly dependent on the composition of the copolyether ester, but al80 on the film thickness. At any chosen film thickne~s tbe water vapour permeability should always be at least lO00 g/m~ day. $t 20 has been found that very favourable results are obtained using a polymer fil~ having a thiokness in the range of 5 to 35 ~m. Optimum results are generally obtained when the thickness of the polymer film is in the range of lO to 25 ~m For the preparation of the copolyether esters to be used in the compo-25 site products according to the present invention reference is made toBritish Patent Specifications 682 866, 1 403 2l0 and 1 404 340. Prefe-rence is given to copolyether esters of which the short-chain units entirely or substantially consist of polybutylene terephthalate units.
Films o~ these copolyether esters are easy to prepare. Moreover, films 30 of this material generally show better physical properties for the present use than film~ of copolyether esters in which for instance ~0~
of the terephthalic acid has been replaced with 2 different dicarbo~ylic acid. For special uses replacem~nt of a s~all percentage of the l,4-butanediol with an other diol and/or replacement of terephthalic acid - 4 - ~KU 1893 R

with an other `1OW mol~cular weight dicarboxylic acid may be of advantage.
Included among low ~olecular weight diols (other than 1,4-butanediol) which are converted into short~chain ester units are acyclic, alicyclic and aromatic dihydroxy compounds~
Preferred are diols ~ith 2-15 carbon atoms such as ethylene, propylene, isobutylene~ pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, and decamethyle~e glycol, dihydroxy cyclohexane, cyclohexane dimethanol, resorcinol, hydroguinone and 1,5-dihydroxy naphthalene~
Especially preferred are aliphatic diols containing ~-8 carbon atoms.
Included among the bis-pbenols which can be used are bislp-hydroxy)di-phenyl, bis(p hydroxyphenyl)methane and bis(p-hydroxyphenyl)propane.
Corresponding ester forming derivatives oE diols are also suitable for use tfor instance epoxy ethane or ethylene carbonate may be used instead of ethylene glycol).
The term ~low molecular weight diolsW as used in the description of the invention also refers to these corresponding ester forming derivatives, the molecular weight requirement relating to the diol as ~uch and not to derivatives thereof.

Suitable dicarboxylic acids (other than terephthalic acid) which are reacted with the ~fore-me~tioned long-chain glycols and with low molecu-lar weight diols to form copolyesters are aliphatic, cycloaliphatic or aromatic dicarboxylic a~ids having a molecular weight not higher than 300. The term dicarboxylic acid used in the description of the invention also refers to equivalents of dicarboxylic acids having two functional carboxyl groups whose behaviour is practically the same as that of the dicarboxylic acids in the conversion with glycols and diols to copoly-esters. These equivalents include esters and ester forming derivati~es, such as the acid halides and anhydrides. The requirements regarding the molecular weight relate to the acid and not to equivalent esters or ester forming derivatives thereof. The dicarboxylic acids may contain randomly substituted groups or combinations which do not detrimentally affect polyester form~tion or the use of the polymer in the compositions according to the invention. Aliphatic dicarboxylic acids, as the term is used herein, are carboxylic acids having two carboxyl groups which are each attached to a saturated carbon atom. Aliphatic or cycloaliphatic acids having coniugated unsaturation often cannot be used because of 9~
- S AKU 1~93 ~

~7inylpol~meri~ation~ ~owever, some unsaturated acids, such as maleic acid? can b~ used~ Aroma~ic dicarboxylic acids, as the term is used herein, are dicarboxylic acids ha~ing two carboxyl groups attached to a carbon atom in an isolated or fused ben~ene ring. It is not necessary that both fuhctional carboxyl groups be attached to the sa~ne aromatic ring and where ~ore than one ring is present, they can be joined by aliphatic or aromatic divalent radica]s or divalent radicals such as -O-or -SO~-O
Preference is given to cyclohexane dicarboxylic acids and adipic acid.
RepresentatiYe aro~atic dicarboxylic acids which can be used include phthalic and isophthalic acids, biben~oic acid~ substituted dicarboxy compounds with two benzene nuclei such a~ bis(p-carboxyphenyl)methane, p-oxytp-carboxyphenyl) benzoic acid, ethylene-bis(p-oxybenzoic acid) l,5~naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,

2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid, an-thracene dicarb~xylic acid, 4,4~-sulfonyl dibenzoic acid and Cl-C12 al~y~ and ring substitution derivatives thereof, such as halo, alkoxy, and aryl derivatives. ~ydroxyl acids such as p(B-hydroxy-ethoxy) ben-zoic acid ca~ also be used providing an aromatic dicarboxylic acid is also present.
Aromatic dicarboxylic acids are a preferred class for preparing the co-polyester polymers of thi~ invention. Among the aromatic ~cids, those with 8-16 car~on atoms are preferred, particularly the phenylene dicar-boxylic acids7 i.e., phthalic and isophthalic acid~.
- 25 The long-chain glycols preferably entirely consist of polyethylene oxideglycol. In so2e cases it may be desirable to make use of random or block copolymers of epo~yethane and minor amounts of a second epoxy alkane. It is preferred that the second monomer should form less than 40 mole % of the polyalkylene oxide glycols and, more preferably, less than ~0 mole %.
Examples of suitable second monomers include l,2- and l,3-epoxy propane, l,2-epoxy butane and tetrahydrofuranO Alternatively, use ~ay be made of mixt~res of polyethylene oxide glycol and a second polyalkylene oxide glycol, such as poly-l,2-propylene oxide glycol or polytetramethylene oxide glycol.

The polymers described herein can be made conveniently by a conventional ester interchange reaction. A preferred procedure involves heating the

3~

~U 1893 R

dimethyl ester of tercphthalic ac:Ld with a loncl chain glycol ~nd a molar excess of 1~4-but~nediol in the presence o a catalyst at 150 to ~0C
ollowed by ~istilling off methanol formed by the interchange~ ~eating is continued until methanol evolution is complete. Depending on tempera-ture, catalyst and glycol excess, this reaction is complete within a fewmlnutes to a few hours. This procedure results in the preparation of a low molecular weight prepolymer which can be carried to a high molecular weight copolyeste~ of thi5 invention by the procedure described below.
Such prepolymers can also be prepared by a number of alternate esterifi-~ation or ester interchange processes; for example, the long-chain glycol can be reacted with a high or low molecular weight short-chain ester homopol~ner or c~polymer in the presence of catalyst until randomization occurs. The short-chain ester homopolymer or copolymer can be prepared by ester interchange from either the dimethyl esters and low molecular lS weight diols, as above, or from the free acids with the diol acetates.
Alternatively, the short-chain ester copolymer can be prepared by direct e~terification f~o~ appropriate acids, anhydrides or acid chlorides, for example, with diols or by otber processes such as reaction of the acids with cyclic ethers or carboDates. Obviously the prepol~er might also be prepared by runniDg these processes in the presence of the long-cha~n glycol.

The resulting prepol~er is then carried to high molecular weigbt by distillation of the excess of short chain diol. This process is known as ~polycondensation~ Additional ester interchange occurs during this distillation to increase the molecular weight and to randomize the arrangement of the copolyester units. Best results are usually obtained i~ this final distillation or polycondensation is run at a pressure not higher than 130 Pa and 240-260C for less than 2 hours in the presence of antioxidants such as sym- di- beta- naphthyl-p~phenylenediamine and 30 1,3,5-trimethyl-2,4,6-tri[3,5-ditertiarybutyl-4-hydroxybenzyl]benzene.
Most practical polymerization techniques rely upon ester interchange to complete tha polymeri~ation reaction. In order to avoid excessive hold time at high te~p~eratures with possible irreversible thermal degrada-tion, it i5 ~dvarltagous tc employ a catalyst for ester interchange reactions. While a wide variety of catalysts can be used, organic tita-nates such as tetrabutyl titanate used alone or in co~bination with - 7 ~ ARU 1893 R

magnesium or calclum acetate ar preferred. Complex titanates, such a~
Mg~HTi(OR)~]2, derived rom alkali or alkaline earth ~etal ~1koxides and titanate esters are also very efective. Inorganic titanates, such as lanthanum titanate, calcium acetate/amtimony trioxide mixtures and lithium and magnesium alkoxides are representative o~ other catalysts which can be used.
The long-cbain glycol used according to the invention Ls always a poly-ethylene oxlde glycol having a molecular weight in the range of 800 to 6000.
When use is made of a polyethy~ene oxide glycol having a molecular weight c 800, the proportion thereof to be incorporated in the copoly-ether ester is prohibitively high. For, a film made therefrom ha~ing a thickness of, say 35 ~Im and a water vapour permeability of at 1east l000 g/m day has been found unsuitable for use in waterproof garments or tents because of its physical properties. Also the manufacture of gar-ment~ ~ro~ copolyether ester films prepared by using a polyethylene oxide glycol having a molecular weight > 6000 leads ~:o unsatisfactory results in t~at the physical properties of the copolyether ester fi~ns are deficient in several respects, e.g. as far as strength is concerned.
Generally, the m~st favourable results are obtained when the long-chain glycol is a polyethylene oxide glycol having a moleculsr weight in the range of l000 to 4000. It has been found that the use of a long-chain glycol ha~ing a ~olecular weight in the range of l000 to 2000 results in obtaining films having very good properties when the percentage short-- 25 chain ester units used is in the range of 60 to 75~ by weight. When,however, the molecular weight of the long-chain glycol is in the range of 2000 to 4000~ then it i5 preferred to use a copolyether ester of which the proportion of short-chain ester units is in the range of 65 to 75% by weight~

For use in the products of the present invention very good results are obtained with copolyether ester films produced by film blowing or flat die extrusion, said films having a water absorption not higher than 17%
by weight, calculated on the weight of the dry films~ measured at 23C
in water in accordance with DIN 53~95.
Preferred to that end is the use of polymers which can be tranformed by .D

- 8 - ~RU 1~93 ~

film blowing into Eilms showing a water absorption not higher than 11%
by weigh~.

The manufacture of films from the present copolyether esters is carried out in the manner known per se from the art, as described in Xirk-Othmer, ~ncyclopedia of Chemical Technology 9 (1966~, pp. 232-241O

By the film blowing pr~cess films may be obtained having a thicknes6 in the range o~ 5 tc 35 ~ m.
Preference, howeYer, is given to films obtained by flat die extrusion on a roll. Preferably, ~he temperature of the roll is chosen between 40 and 120C, A8 described in US Patent Specification 3 968 183~ -The films made in the above-described way generally have a lo-~er absorp-tion capacity than the films obtained by, for instance, compression moulding.

The copolyester film may be attached to the porou~ te~tile material in 1~ various ways, which may include a heat treatment, sewing or the use of an adhesive. Alternatively, the copolyester film may be enclosed by two layers of textilc l~aterials, leading to a construction of at least three layers.
The adhesive to be used is not only dependent on the composition of the 20 copolyether ester, but also on the type of substrate~ It has been found that generally favourable results are obtained by using a bicc ~nent glue. The one component of this glue is forn!ed by a prepolymer having -NCO-containing endgroups and the other component by a prepolymer having O~-endgroups. The bicomponent glue is applied to the film and/or the 25 cloth with the aid of a screen roll ro~ a solution, e.gO in ethyl acetate 9 followed by bonding upon evaporation of the solvent.
In this way a windproof material i~ obtained ha~ing a water ~apour permeability of as high as at least 1000, but preferably exceeding 2000 g/m day. The inqention will be further described in the following 30 examples, which a~e of course not to be construed as li~iting in any manner the scope thereof. All parts and percentages mentioned in this application are by weight, unless otherwise indicated.

The follo~ing methods were used for deter~ining the properties of the ~ ~3~ .D

~ g A~U lag3 R
-copolyether este~ fllms and/or the composite products according to the invention.

A. Determination of absorption in water Bt 23C in accordance with DIN
53495.
B. ~etermination of water vapour permeability at 30C ~nd 50~ RH in accordance with ASTM E96-66 (Procedure B).
C. Determination of waterproofness wLth a modifled Sutter's test appa ratus and by the Mullin's ~urst Test~ which two tests are described in the afore~entioned British Patent Specification 2 024 100.

In the Sutter test the waterproofness is determined ~isually. The test procedure includes subjecting the copolyether ester film to a hydr~-static head of 2S cm of wa~er over a period o~ 20 minutes~
In the Mullin~s Burst Test the waterproofness is also determined visual-ly~ For 10 seconds a particular pressure is applied, which is subse~
quently maintained for 30 seconds.
~ superatmo6pheric pressure level of abQut 213 kPa (2,1 a~ .eres gauge pressure) is used as an acceptance level for the use envisagedO

E~ample I
Into a 200-1 a~toclave there were introduced 33,3 kg of dimethyl tere-20 phthalate, 21,6 kg of 1,4-butanediol and 12,5 kg of polyethylene oxide - glycol having an average molecular weight o~ 4000. The reaction mixture was heated to 110C, wi~h ~tirring, followed by adding 500 ppm of tetra-butyl titanate, calculated on dimethyl terephthalate. ~pon a further increase in temperature to 160C methanol distilled off, after which the pressure was slowly reduced to 100 ~a and the temperature increased to 245C.
This polycondensation reaction, which lasted 3 to 4 hours, led to a pro-duct having a relative viscosity of 2,53 (measured on a concentration of 1 g in 100 g of m-cresol at 25C).
In the same way as indicated above several copolyether esters were pre-pared using varying amounts of the above-mentioned polyethylene oxide glycols and polyet~lene oxide glycols having molecular weights of lO00 and 2000.

~ 10 - ~X~ lB93 R

The co~olyether esters prepared had the foll~wing compo~itlon:

W~.~ short-chain ~olecular weight poly--ester unit~ ethylene oxide glycol (PEG) n rel A 74,2 4000 2,53 B 69~0 4000 2,76 C 63,8 ~00~ 2,86 D 58,7 4000 3,04 a, 0 2000 2,~1 F 66 lO00 2,50 Example II
The copolyether esters prepared in ~xample I were subjected to post-condensation in the solid state up to a relative viscosity between 3,5 and 4 and transformed by film blowing into films having a thickness ranging from lO to 30 ~m, aftar which the water absorption of the films was measured in wa~er at 23C in accordance with DIN 53495u The results are given in Table I.
Table l ~polyether esterWater absorption (wt.

~ 11 E

The ilms were subsequently laminated with a polyamide 6 fabric and made into garments ~anoraks). The reactions of participants in a wearing test were very favourable.

Example III
The copolyether esters prepared in Example I were again postcondensa-t~d ~n the solid state up to a relative viscosity between 3,5 and 4had been obtained, tranformed by film blowing into fil~s having the thicknesses given in the table belo~ ~f these films the water vapour ~ A~U 18g3 n permeabil~ty ~W~P) was measured at 30C and 50~ R~ in accordance with procedure B of AS M ~96-66.
The results are given in the table below.
Table 2 Copolyeth2r ester fil~ thi~kness (in ~m) WVP ~g/m .24 hr) 1~ 2~00 19 ~0~0 C 18 23~0 2~00 28 ~ 1950 B li 1800 1~0~
~ 11 2080 The above table cl~arly shows that with the percentage of short-chain ester unit~ remaining the same, the WVP increases with increasing mole-cular we~ght of ~he polyethylene oxide glycolO

Example IV
Of the films prepared in Example III the water proofness was measured in the same way as indicated before at a pressure in the range of 5 to 400 k~a.
Visually assessed, none of the fi}ms A through F tested were found to be permeable to water.

Example V
The polymer~ B, C and D of Example I having butylene terephthalate units ~BTP) as sbort-chain ester units were compression moulded into films, after which the water vapour permeability twvp) and the water absorption were deter~ined in the before-indicated manner.
The propert~es of these films were compared with those of similarly pre-pared films with ethylene terephthalate units ~ETP~ as short-chain ester units.

lls~L~
1~ A~U l8~3 R

~he molecular welgh~ ~ the polyethylene oxide glycols used in all the ~olymers was 4000.
The result~ of the measurements are given in the table below.
Table 3 Poly- ~t.~ BTP, film thlck- wVP (g/m water absorp mer and ETP ~rel ness ~ m) 24 hr) tion ~wt.%~

B 69,0 BTP 2,75 80 1060 16 P 63~8 F.TP 2,00 60 1280 29 C 63/3 BTP 2,86 73 1470 21 Q 58,7 ~TP 2, 2~ 68 1240 35 D 58,7 BTP 3~04 ~9 lS20 28 R 48,4 ~TP 2,lR - - 54 The results in the table above show that the water absorption of the polymer films P and Q, of which the short~chain e~ter units are ethylene terephthalate units, i~ considerably higher than that of the polymer film~ C and D of si~ilar compositions, bu~ with butylene terephthalate units as short-chain este~ units~
Surprisingly, the water vapour permeabili~y of the films P and Q iB
considerably lower than that o the similar polymers C and ~. From a comparison with Table 1 it also appears that the water absorption o~
.- compression moulded films is ~ar higher than that of films obtained by the film blowing process.

~xample Vl A series of films were flat-die extruded from copolyether esters having butylene t~repbthalate units (BTP) or ethylene terephthalate units ~ETP) as short-chain ester units and polyethylene oxide glycol ~PEG) having a molecular weight of 4000 as polyethe~ One copolyether e~ter moreover contained polytetramethylene oxide (PTMG) having a molecular weight of 1000.
Of the films thus obtained the water vapour permeability and the wa~er absorption were determined in the above-indicated way.

- 13 ~ AKU 1893 R

Tha measurlng results are listed in the table below.

Table 3 Poly~ wt.~ sTp fil;m ~hick- wVp tg/m water absorp-mer or ETP polyether ness (~) 24 hrs) tion twt.~) ~ 57,7 BTP 75 wt.~ PEG 19,3 1830 19 25 wt.% PTMG
L 63,~ E~P 100~ PEG 11,1 1780 25 M 69 BTP 100~ PEG 1915 1630 14 N 69 ~TP 100~ PEG l9,B 1280 21 The above table clearly shows that at a similar thickness films obtained from copolyether esters with ethyle~e terephthala~e units as short-chain ester units inv~riably display a higher water absosption and a lower water vapour per~eability than fiLms made from copolyether esters with butylene terephthalate units as short-chain ester units. The above table 5 al50 ~hows tha~ par~ial repl~c~--n~ (up to 30~ by weiyht) of the PEG
4000 with a polyalkyle~e o~ide glycol having a hi~her ato~ic carbon to oxygen ratio than 2,4, such as PTMG, leads to a film having a very good water vapo~r per~eability, but a somewbat higher water absorption than that of a film frvm a copolyether ester containing a similar weight - 20 percentage of PEG but no PTMG (polymer M).

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Flexible layered product for use in waterproof garments or tents of textile material covered with a waterproof material having a water vapour transmission rate of at Least 1000 g/m day, characterized in that the textile material is covered with a film of a copolyether ester consisting of a plurality of recurrent intralinear long-chain ester units and short-chain ester units which are randomly joined head-to-tail through ester bonds, said long-chain ester units corre-sponding to the formula:

and said short-chain ester units corresponding to the formula:

where G is a divalent radical radical after removal of terminal hydroxyl groups from at least one long-chain glycol having a molecu-lar weight in the range of 800 to 6000 and an atomic ratio of carbon to oxygen in the range of 2,0 to 4,3, at least 70% by weight of the long-chain glycol having a carbon to oxygen ratio in the range of 2,0 to 2,4, R is a divalent radical remaining after removal of carboxyl groups from at least one carboxylic acid having a molecular weight less than 300, and D is a divalent radical remaining after removal of hydroxyl groups from at least one diol having a molecular weight less than 250, at least 80 mole % of the dicarboxylic acid used consisting of terephthalic acid or the ester forming equivalents thereof and at least 80 mole % of the low molecular weight diol consisting of 11 4-butanediol or the ester forming equivalents thereof, the sum of the mole percentages of the dicarboxylic acid which is not terephthalic acid or the ester forming equivalents thereof and of the low molecu-lar weight diol which is not 1,4-butanediol or the ester forming equivalents thereof is not higher than 20 and the short-chain ester units form 50-75% by weight of the copolyether ester.

2. A product according to claim 1, characterized in that the textile material is hydrophobic.

3. A product according to claim 1, characterized in that the thickness of the polymer film is in the range of S to 35 µm, preferably 10 to 25 µm.

4. A product according to claim 1, characterized in that the short-chain ester units of the copolyether ester substantially consist of poly-butylene tereplthalate units.

5. A product according to claim 1, characterized in that the copolyether ester contains a long-chain glycol consisting of polyethylene oxide glycol having a molecular weight in the range of 1000 to 4000.

6. A product according to claim 1, characterized in that at a molecular weight of the long-chain glycol between 1000 and 2000 the proportion of the short-chain ester units in the copolyether ester is in the range of 60 to 75% by weight.

7. A product according to claims 1, characterized in that at a molecular weight of the long-chain glycol between 2000 and 4000 the proportion of the short-chain ester units in the copolyether ester is in the range of 65 to 75% by weight.

8. A product according to claim 1, characterized in that use is made of copolyether ester films produced by film blowing or flat die extru-sion, said films having a water absorption not higher than 17% by weight, calculated on the weight of the dry films, measured at 23°C
in water in accordance with DIN 53495.

9. A product according to claim 8, characterized in that the water absorption is not higher than 11% by weight.