WO1994019178A1

WO1994019178A1 - Laminate made of a textile material and a water vapour permeable film

Info

Publication number: WO1994019178A1
Application number: PCT/EP1994/000258
Authority: WO
Inventors: Henricus Joannes Maria Van De Ven
Original assignee: Akzo Nobel N.V.
Priority date: 1993-02-16
Filing date: 1994-01-29
Publication date: 1994-09-01
Also published as: EP0684904A1; JPH08507728A

Abstract

A laminate made of a textile material and a water vapour permeable film is characterized in that the water vapour-permeable film is bonded to a nonwoven fabric made of permanent hydrophilic fibers.

Description

Laminate from a textile material and

a water vapor permeable film

Description:

The invention relates to a laminate made of a textile

Material, namely a fleece and a water vapor permeable film, the use of the laminate and its production.

It is known to combine a textile material with a water vapor permeable waterproof film. Such a product is described in EP-B2-0 111 360. The film consists of a copolyetherester, the textile material is a hydrophobically finished fabric.

Such products are e.g. in the manufacture of textiles namely clothing or tents

used. However, it has been shown that although the laminate used is provided with a water-vapor-permeable waterproof film, difficulties arise when the textile is suddenly to release a large amount of water vapor to the outside.

This is particularly the case with clothing if the wearer of the textile suddenly starts to sweat profusely or if very large quantities are present in a tent

Water vapor is created, for example because there are many people in the tent who are sweating, or if water vapor is generated in some other way.

Then there may be a build-up of water vapor on the inside of the water vapor permeable film. The textile therefore feels moist from the inside, which is unpleasant for the wearer of the textile; in a tent

the moisture accumulates, which is also associated with unpleasant side effects. In addition, water vapor can condense, which is also a major disadvantage.

There is therefore still a need for improved water vapor-permeable products which do not have the disadvantages mentioned above.

The object of the invention is therefore to provide a laminate which is able to absorb suddenly larger amounts of water vapor, e.g. It is better to drain sweat outwards It is also an object of the invention to provide a material which can be produced in a simple, economical manner and which is good

can be processed, especially for the production of water vapor permeable watertight Clothing such as rainwear, sportswear, coats, shoes and for the manufacture of tents,

Mattress protectors and the like suitable is.

This object is achieved by a laminate according to claim 1. In the claims 2 to 9 particularly advantageous embodiments of the invention are given. The invention further relates to a method for

Production of such laminates and the use of the same, as specified in claim 10 and claims 11 to 12.

The water vapor permeable waterproof film can in principle consist of any synthetic polymer that gives the film sufficient water vapor permeability while being water impermeable. These include films made of polytetrafluoroethylene, polyetherimide esters such as those e.g. are described in European Patent No. 0 322 777, and polyether amides, polyether urethanes and the like.

However, preference is given to using films which are composed of a synthetic polymer based on copolyether esters, i.e. Polymers derived from longer chain polyglycols, short chain glycols, e.g. with 2 to 4

Derive carbon atoms and dicarboxylic acids. These are primarily films based on a

Copolyetherester, which consists of a variety of recurring intralinear long-chain and short-chain

There are ester units which are statistically linked head to tail via ester linkages, the long-chain ester units of the formula

- O - G - O - C - R - C - and the short chain ester units of the formula

- O - D - O - C - R - C -, in which G represents a divalent radical which, after removal of terminal hydroxyl groups from at least one long-chain glycol, has an average molecular weight of 600 to 6000 and an atomic ratio of carbon to oxygen between 2 , 0 and 4.3 remains, with at least 20% by weight of the long-chain glycol having an atomic ratio of carbon to oxygen between 2.0 and 2.4 and 15 to 50% by weight of the

Make up a copolyetherester, R represents a divalent radical that remains after the removal of carboxyl groups from at least one dicarboxylic acid with a molecular weight of less than 300, and D represents a divalent radical that after removal of hydroxyl groups from at least one diol with a molecular weight of less than 250 remains, wherein at least 80 mole percent of the dicarboxylic acid used consists of terephthalic acid or its ester-forming equivalents and at least 80 mole percent of the small molecular weight diol consists of 1,4-butanediol or its ester-forming equivalents, the sum of the mole percent of the dicarboxylic acid that is not terephthalic acid or its ester-forming equivalents Equivalents, and the diol with a small molecular weight that is not 1,4-butanediol or its ester-forming equivalents is at most 20 and the short-chain ester units are 40-80% by weight of the copolyether ester.

Waterproof, water vapor permeable are preferred

Films which have no pores, that is to say have a non-porous structure, which means that the film is neither porous nor microporous.

The fibers that make up the fleece are permanently hydrophilic. The fibers are preferably fibers made of synthetic polymers. In principle, all synthetic polymers are suitable here which are inherently hydrophilic or in the case of corresponding ones

Treatment has achieved permanent hydrophilicity. This permanent hydrophilicity can be achieved by incorporating appropriate additives, which are the polymer

impart hydrophilic properties.

One possibility is hydrophilic polyester fibers, as described in German patent application P 27 55 341.9.

Hydrophilic fibers, as can be used according to the invention, are also available from hydrophobic fibers, provided that they are given the appropriate permanent finish. This can be done, for example, by coating it with a film of hydrophilic material. It is important that the hydrophilicity is permanent, ie that the textile does not lose its hydrophilicity even if the wearer sweats a lot, and if it is washed frequently. Hydrophilic fibers made from a polymer based on copolyether esters are particularly suitable, it being particularly advantageous if both the water-vapor-permeable film and the hydrophilic fibers consist of copolyether esters which have the same or only slightly modified chemical composition.

Although synthetic polymers such as copolyether esters and others are preferred, it is also possible to use nonwovens made of fibers which consist wholly or partly of fibers based on cellulose or modified cellulose, provided that these fibers have a corresponding hydrophilicity.

Permanently hydrophilic fibers that can adsorb water when high or high are particularly suitable

Moisture is present, e.g. as a result of profuse sweating, which, however, releases the water again by desorption as soon as the ambient humidity has decreased.

Although nonwovens made of fibers based on copolyether esters are preferred, it has proven to be particularly advantageous if these fibers are processed to form a nonwoven in a mixture of hydrophobic fibers, in particular polyester fibers, and then used according to the invention to build up the laminate. Mixtures with a small proportion such as about 5% are already suitable, with fractions of 15-25% (weight percent) being preferred. However, higher proportions such as 50% can be used.

In a particularly advantageous embodiment of the

Laminates according to the invention is the polymer from which the waterproof, water vapor permeable film and / or the permanently hydrophilic fibers are formed, in whole or in part, a copolyether ester, in which at least 70 mol% of the dicarboxylic acid used is 2,6-naphthalenedicarboxylic acid or its ester-forming equivalents and in which at least 70 mol% of the diol used has a small molecular weight of 1.4 -Butanediol or its ester-forming equivalents and the sum of the molar percent of the

Dicarboxylic acid which is not 2,6-naphthalenedicarboxylic acid or its ester-forming equivalents and the diol with a small molecular weight which is not 1,4-butanediol or its ester-forming equivalents is at most 30% and the ester units with short chains are 35 to 80 Make up% by weight of the copolyether ester.

A copolyetherester which consists of a multiplicity of recurring intralinear long-chain and short-chain ester units which are statistically linked head to tail via ester linkages is very particularly suitable, the long-chain ester units of the formula

- O - G - O - C - R - C - and the short chain ester units of the formula

- O - D - O - C - R - C -, where G represents a divalent radical, which after removal of terminal hydroxyl groups from at least one long chain glycol of a medium

Molecular weight of 600 to 4000 and an atomic ratio of carbon: oxygen between 2 and 4.3 remains, wherein at least 20 percent by weight of the long-chain glycol have an atomic ratio of carbon: oxygen between 2.0 and 2.4 and

15 to 50 percent by weight of the copolyetherester, R represents a divalent radical which remains after the removal of carboxyl groups from at least one dicarboxylic acid of a molecular weight of less than 300 and

D represents a divalent radical which remains after the removal of hydroxyl groups from at least one diol of a molecular weight of less than 250, with at least 70 mol% of the dicarboxylic acid used

2,6-naphthalenedicarboxylic acid or its ester-forming

Equivalents exist and at least 70 mol% of the diol with the low molecular weight consists of 1,4 butanediol or its ester-forming equivalents and the sum of the mol percent of the dicarboxylic acid, which is not 2,6-naphthalenedicarboxylic acid or its ester-forming equivalents, and of the diol a small molecular weight that is no

1,4-butanediol or its ester-forming equivalents is at most 30% and the ester units with short chains are 35 to 80% by weight of the copolyetherester.

Such copolyether esters are described in Dutch patent application No. 9300723 dated April 28, 1993

described; the disclosure in this patent application is expressly referred to here.

The fleece according to the invention is preferably a fleece made from staple fibers. The fleeces can on itself known way. Needled nonwovens are preferably used.

More details on the manufacture of corresponding

Nonwovens include the book "Manual of Nonwovens by

Radko Krcma W.R.C. Smith Publishing Co., Atlanta USA 1971.

The fleece can be bound using conventional binders. Polyacrylate-based binders should be mentioned here in particular. However, it is also possible to thermally bind the nonwovens. It goes without saying that when tying the fibers care is taken that the fleece largely retains its hydrophilicity when tied.

Nonwovens made from staple fibers are preferred, but nonwovens made from continuous filaments can also be used, but care must be taken to ensure that the nonwovens have sufficient bulk.

The water vapor permeability of the film should be at least about 1000 g / m ² .day. The thickness of the membranes can also be varied within a wide range, for example within 5 to 35 μm, preferably from 10 to 25 μm. The thickness to be selected also depends on the application; a suitable thickness can be selected by the average person skilled in the art with a few trials. The main issue here is the extent to which the film is exposed to mechanical stress; the thinner the film, the more sensitive it becomes, of course

mechanical influences. The thickness of the nonwovens is generally 1 to 10 mm. The connection between the membrane and the fleece can be produced by customary methods. Preferred is a point-like or small-area binding with the aid of a binder, since in this way as much free area of the membrane as possible for the passage of water vapor

Is available, i.e. as much porosity or

Permeability is maintained.

Here, gravure printing with binders dissolved in a solvent is particularly suitable. The lamination can also take place according to the so-called screen printing process, using aqueous dispersions

reach. A thermal connection is also possible, the methods of powder technology to be mentioned here, the use of hot melt adhesives and the like.

The titer of the fibers used for nonwovens should be as fine as possible and is generally between about 0.5

up to 4.5 dtex.

It was particularly surprising that it is possible with the laminate according to the invention to pass on water vapor if it suddenly arises in large quantities, as is the case, for example, with intense sweating, sweating, etc. Although the reasons for this have not yet been clarified, it appears that the nonwoven is able to absorb and store water vapor that cannot immediately escape through the water vapor permeable membrane in such a way that the backing of the textile does so Has the feeling that the sweat or water vapor has already been completely removed. The excess water vapor or excess sweat may be in vapor form in the The fleece is stored and then gradually released through the membrane. It is also possible that the nonwoven initially absorbs some of the water vapor in the fiber and then passes it on to the outside in the form of water vapor at a later point in time. When the laminates according to the invention are used in textiles, the wearing comfort is improved in a special way, so that the textile can be worn very comfortably even under great loads. In the case of tents, there is no strong accumulation of water vapor inside the tent, so that comfort is also considerably improved here, if larger

Amounts of water vapor are generated.

The laminates can be produced in a very simple manner. The laminate is very versatile. It is especially suitable for the production of

Clothing, in particular sporting goods, rainwear, coats, shoes and for the manufacture of tents and mattress protectors.

The invention is illustrated by the following examples.

A card is used to produce a fleece from three different types of fibers, which is then needled in the usual way.

The fleeces consist of staple fibers with a titer of 1.7 dtex and a staple length of 40 mm.

Composition fleece 1: 100% polyethylene terephthalate fibers Fleece 2: mixture of 20 wt.% Polyethylene terephthalate fibers and 80% of a copolyetherester fiber made from a copolyetherester according to Example 1B of EP-B2-0 111 360 Fleece 3: Mixture of 50% by weight of a polyethylene terephthalate fiber and 50% by weight of a copolyetherester fiber, as used in fleece 2.

The nonwovens are each laminated with a copolyetherester membrane, the copolyetherester membrane having the same chemical composition as the copolyetherester fibers.

The lamination is carried out using the gravure printing process, using a solvent-containing two-component polyurethane adhesive (Saba Type 5622, a

Product of Saba, Dinxberlo, the Netherlands).

The water vapor absorption on the laminates is measured according to the following method: This much is in a round glass jar

Given water that there is a distance of 25 mm between the surface of the water and the edge of the vessel. The laminates are placed on the glass vessel with the fleece side facing the water. The temperature in the measuring room is 21 ° C, the relative humidity 65%. Measurements are carried out at two water temperatures, namely at 30 ° and at 40 ° C. The measurement results are summarized in the following table. It can be seen that fleece made from 20% by weight

Polyethylene terephthalate and 80% copolyetherester fibers show excellent moisture absorption, the samples were each exposed to the influence of moisture for 4 hours.

Claims

Laminate of a textile material and a water vapor permeable film

1. Laminate of a textile material and a water vapor permeable waterproof film, characterized in that the water vapor permeable waterproof film is connected to a nonwoven made of permanently hydrophilic fibers.

2. Laminate according to claim 1, characterized in that the film made of a synthetic polymer based

Copolyetherester exists.

3. Laminate according to claim 1 or 2, characterized in that the permanently hydrophilic fibers consist of a polymer based on copolyetherester.

4. Laminate according to one of claims 1 to 3, characterized

characterized in that the fleece consists of a mixture of permanently hydrophilic fibers and hydrophobic fibers.

5. Laminate according to claim 5, characterized in that the hydrophobic fibers are polyester fibers.

6. Laminate according to one of claims 1 to 5, characterized

characterized in that the permanently hydrophilic fiber is a polyester fiber which has been obtained by preparing a polyester composition which contains 1 to 20 percent by weight of one or more oxalate complexes of the general formula

Me _n [Z (C ₂ O ₄ ) _m ] is obtained, spun, the thread obtained is stretched and at temperatures in the range from 90 to 170 ° C. in

Hydrofixed in the presence of liquid water, where:

Me: at least one of the ions Li, Na, K, Rb, Cs

or NH ₄

Z: at least one complex-forming central atom from the group Mg, Ca, Sr, Ba, Zr, Hf, Ce, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, B, AI, Ga, In, Sn , Pb and Sb n: 1, 2, 3 or 4 and m: 2, 3 or 4.

7. Laminate according to claim 1 or 2, characterized in that the permanently hydrophilic fiber consists of a hydrophobic fiber which has been made permanently hydrophilic by permanent equipment.

8. Laminate according to one of claims 1 to 7, characterized in that the waterproof, water vapor permeable film has a non-porous structure.

9. Laminate according to one of claims 1 to 8, characterized

characterized in that the polymer from which the waterproof, water vapor-permeable film and / or the permanently hydrophilic fibers are formed, is wholly or partly a copolyether ester, wherein at least

70 mol% of the dicarboxylic acid used is 2,6-naphthalenedicarboxylic acid or its ester-forming equivalents, and at least 70 mol. % of the diol with a small molecular weight used is 1,4-butanediol or its ester-forming equivalents and the sum of the molar percentages of the dicarboxylic acid which is not 2,6-naphthalenedicarboxylic acid or its ester-forming equivalents and of the diol with a small molecular weight, that no 1,4-butanediol or its ester-forming

Equivalents is, at most 30% and the ester units with short chains make up 35 to 80% by weight of the copolyether ester.

10. A process for the production of laminates according to claim 1, characterized in that a nonwoven fabric is made from permanently hydrophilic fibers and combines this with a water vapor permeable film.

11. Use of the laminates according to one or more of the

Claims 1 to 9 for the manufacture of clothing.

12. Use of the laminates according to one or more of the

Claims 1 to 9 for the manufacture of mattress protectors.