EP0151170B1 - Protection tarpaulin fabric and manufacturing method thereof - Google Patents

Abstract

The protection tarpaulin fabric is water-tight, heat reflecting, has a plurality of layers, is comprised of a light tear-resistant polyester cloth of 160 g/m2 at the maximum as base cloth, provided on one face with at least one layer pigmented with a cross-linked polyacrylic acid ester and with a covering layer comprised of polyurethane, the coatings representing in total from 25 to 80 g/m2. Essentially pigments which reflect heat are used, such as particularly pigments derived from aluminium or aluminium bronze. Furthermore, in the process for manufacturing the protection tarpaulin fabric according to the present invention, which is characterized in that on a light optionally pretreated polyester cloth of 160 g/m2 at the maximum and used as a base cloth at least one layer is applied on one face by means of an aqueous pigmented cross-linkable polyacrylic acid ester dispersion as well as a covering layer of polyurethane, preferably an aliphatic polyurethane with utilization of usual auxiliary agents and intermediary drying, the application of solid material during the various coatings being such that the finished protection tarpaulin fabric comprises a deposit of solid material on the base cloth ranging from 25 to 80 g/m2.

Description

The invention relates to a waterproof, heat-reflecting tarpaulin material and a method for its production.

According to the prior art, the waterproofing of heavy fabrics is carried out in a customary manner in a two- or multi-bath process, a water-insoluble metal soap being produced on the goods and the fabric pores being additionally closed by fillers and paraffin or the like (see W. Bernard, "Finishing der Textilien ", 2nd edition 1967, Springer-Verlag, pages 326 ff). Absolutely watertight fabrics can be obtained by coating, using as coating agent, among other things. Polyvinyl chloride is used.

According to this prior art, finished fabrics with at least 300 g / m ² are obtained. The tarpaulins or tarpaulins made from it have a high weight and are difficult to stow, so generally speaking they have the disadvantage of cumbersome handling.

The invention is therefore based on the object of providing waterproof, heat-reflecting tarpaulin fabrics which are distinguished by a low overall weight.

According to the invention, this object is achieved in that a polyester lightweight fabric of maximum 160 g / m ^{2 is provided on} one side with at least one pigment-containing layer of a crosslinked polyacrylic acid ester and a cover layer made of polyurethane, preferably aliphatic polyurethane, the coatings being a total of 25 to 80 make up g / m ² .

Accordingly, the process according to the invention for producing waterproof, heat-reflecting tarpaulin fabrics is characterized in that, on an optionally pretreated polyester lightweight fabric of at most 160 g / m ² as the base fabric, at least one line (corresponding to one layer) is crosslinkable by means of an aqueous, pigment-containing one Polyacrylic acid ester dispersion and a top coat using a polyurethane, preferably aliphatic polyurethane, are applied with the use of customary auxiliaries, with intermediate drying, with only enough solid being applied during the individual coats that the finished tarpaulin material contains 25 to 80 g / m ^{2 of} solid support on the base fabric.

Polyester lightweight fabric has proven to be particularly suitable as the base fabric for the protective tarpaulin fabrics according to the invention, although the same can also be reinforced by small amounts of aramid threads. Lightweight fabrics are to be understood to mean those whose square meter weight is between 80 and 160 g, in particular between 90 and 120 g. Protective tarpaulin fabrics with a particularly smooth surface are obtained if a light polyester filament fabric is used as the base fabric, which is why this type of fabric is particularly preferred.

The crosslinkable polyacrylic acid esters that can be used are known from the prior art. The crosslinkable polyacrylic acid esters contain as reactive groups e.g. N-methylol groups, especially carboxamide methylol groups. Etherified N-methylol groups, where alcohols containing one to three carbon atoms, in particular methanol, have been used for the etherification, are also suitable as crosslinkable groups. The monomers which carry these crosslinkable groups are generally known. N-addition products of formaldehyde with methacrylamide or acrylamide and allyl or methallyl carbamate may be mentioned.

The crosslinkable polyacrylic acid esters can also be used as reactive groups e.g. Contain glycidyl residues. These comonomers are also well known. An example is allyglycidyl ether.

The term crosslinkable polyacrylic acid esters are also - and this group of copolymers is preferred - to be understood as meaning those which contain reactive comonomers which have a suitable curing or crosslinking agent, e.g. Need conventional silanes and / or siloxanes containing amino resins or amino groups. Examples of such comonomers are those which have free OH groups, e.g. 2-hydroxyethyl and 3-hydroxypropyl acrylate or methacrylate. Unsaturated carboxylic acids, e.g. Acrylic acid and methacrylic acid and their amides lead to crosslinked polyacrylic acid esters with aminoplast resins. The latter are very preferably polymerized in, since these protective tarpaulin materials with these coatings are characterized by a particularly good overall result.

Of course, the copolymers used can also contain several of the comonomers mentioned. The amounts of comonomers with crosslinkable groups are about 1.0 to 15, in particular 2 to 10,% by weight, based on the copolymer as a whole.

The monomers also contained in the polyacrylic acid esters are also known. In addition to methacrylic or acrylic acid esters, for example methacrylic or acrylic acid esters of alcohols having one to eight carbon atoms, such as methanol, ethanol, butanol, isobutanol or 2-ethylhexanol, which are generally obtained in amounts of 45-99.0% by weight on the entire polyacrylic ester copolymer, other comonomers, for example vinyl acetate, ethylene, styrene, vinyl chloride and particularly preferably acrylonitrile, are copolymerized in the polymers used. These comonomers are in amounts up to 40 % By weight, based on the total polymer, contained.

The crosslinkable polyacrylic acid esters described come on the market in the form of about 30-70% by weight dispersions.

Pigments are mixed into the cross-linkable polyacrylic acid ester dispersions, which promote heat reflection. Metal powders are particularly suitable as such pigments. Examples of metals that can be mentioned are aluminum, nickel, silver, zinc and alloys such as brass, bronze, aluminum-bronze and the like. Aluminum and aluminum-bronze are preferred for economic reasons. In addition, there are also other heat-reflecting pigments, e.g. Polyester flicker or mica are very suitable. The amount of pigment can vary within wide limits. Already 5% by weight, based on crosslinked polyacrylic acid esters, has a clear effect. It preferably contains 8-30% by weight, particularly preferably 10-25% by weight, based on crosslinked polyacrylic acid esters. The upper limit is determined by economic considerations, but also by decreasing adhesion and fastness to rubbing of the polymer film, and is approximately 60% by weight, based on crosslinked polyacrylic acid esters. If two or more coats of crosslinkable polyacrylic acid ester are used, it has proven useful to mix only a small amount of pigment, about a quarter to a third of the total amount of pigment, with the first coat and to incorporate the predominant amount of pigment into the second and further coats , as this significantly improves the film's adhesion. However, it is also possible to do without the pigment addition in the first stroke, but this method of working is less suitable.

The polyurethanes used for the top coat also belong to the prior art. It is therefore not necessary to go into these connections in more detail. Alipathic polyurethanes are particularly suitable because they have improved light fastness. The top coat can be done either from an aqueous or organic medium. The raw polyester lightweight fabrics are washed in a known manner and then optionally pretreated as usual. The pre-treatment slightly improves the film adhesion.

The coating itself is also carried out in a known manner. For this purpose, the light polyester base fabric is coated on one side with at least one line of the pigment-containing polyacrylic acid ester and then dried. It is particularly preferred to work with two layers of polyacrylic acid ester, the small amounts required being applied preferably by means of an air knife. Then the polyurethane is used as a top coat; also preferably applied with an air knife (for further details see examples). Of course, the usual auxiliaries such as crosslinking agents, thickeners, pH regulators, etc. are also used in the application. Also the simultaneous use of conventional aminoplast resins, water repellents, color pigments and. Similar ones are easily possible and, from case to case, also expedient and advantageous. The amounts of such additives are known to the person skilled in the art.

In the manner described, a protective tarpaulin material is obtained which is distinguished from the known products by remarkable, surprising advantages. Because of the state of the art it was not to be expected that it would be possible to produce such a light yet mechanically strong protective tarpaulin material. In particular, the special base fabric used and the addition of the heat-reflecting pigments to the crosslinkable polyacrylic acid esters make it possible to manufacture the advantageous tarpaulin fabrics in a simple manner. This is not only characterized by its high strength and low weight, but also leaves nothing to be desired in terms of water resistance and heat reflection. The articles made from it, especially tarpaulins, allow easy handling and are therefore easy to use.

example 1

A polyester filament fabric (110 g / m ² ) is prewashed in the customary manner (2 g / 1 anionic wetting agent, 2 g / 1 calcined soda and 3 g / l phosphate complexing agent), rinsed at 90 ^° C. for 20 minutes and dried and 60 seconds at 190 ° C heat set.

• 20 ml/1 Netzmittel auf Basis C_3-4-Alkohole,
• 40 g/1 einer nichtionogenen Copolymerisatdispersion auf der Basis Vinylacetatpropionat (ca. 35%ig),
• 40 g/1 eines handelsüblichen Schiebefestmittels auf Basis Kieselsol/basischer Aluminiumchloridlösung und
• 60 g/I eines handelsüblichen nichtionogenen schimmelfestmachenden Mittels (Aktivsubstanz ca. 10 Gew.%)
• und bei 100° C getrocknet.

The fabric is then pre-fouled with the following aqueous liquor

• 20 ml / 1 wetting agent based on C _3-4 alcohols,
• 40 g / 1 of a nonionic copolymer dispersion based on vinyl acetate propionate (approx. 35%),
• 40 g / 1 of a commercially available sliding solid based on silica sol / basic aluminum chloride solution and
• 60 g / l of a commercially available nonionic mold-fixing agent (active substance approx. 10% by weight)
• and dried at 100 ° C.

The coating is carried out in three layers by means of an air knife, a total solid coating of 40 g / m ^{2 being} obtained.

• 1000 GT (= Gewichtsteile) einer 50%zigen anionischen, vernetzbaren Polyacrylsäureesterdispersion (hergestellt durch Emulsionspolymerisation aus Acrylsäurebutylester, Acrylnitril und Acrylsäure im Gewichtsverhältnis 85,5: 10: 4,5, teilneutralisiert mit Ammoniak auf eine Viskosität von ca. 2000 mPa.s bei 25° C),
• 80 GT einer ca. 80%igen Lösung von Pentamethylolmelaminnethylether,
• 80 GT eines handelsüblichen Imprägniermittels auf Basis eines fettmodifizierten Ethylenharnstoffharzes,
• 25 GT konzentrierter Ammoniak und
• 50 GT Aluminiumpulver (Korngröße durchschnittlich 30µm),
• wobei der pH-Wert nicht über 7 liegen soll.

The following paste is used for the first stroke, applied with a squeegee:

• 1000 GT (= parts by weight) of a 50% anionic, crosslinkable polyacrylic ester dispersion (produced by Emulsion polymerization of butyl acrylate, acrylonitrile and acrylic acid in a weight ratio of 85.5: 10: 4.5, partially neutralized with ammonia to a viscosity of approx. 2000 mPa.s at 25 ° C),
• 80 pbw of an approximately 80% solution of pentamethylol melamine methyl ether,
• 80 pbw of a commercial impregnating agent based on a fat-modified ethylene urea resin,
• 25 GT concentrated ammonia and
• 50 GT aluminum powder (average grain size 30 µm),
• the pH should not be above 7.

After drying at 130 ° C, the second coat is also applied with a doctor blade using the same paste, which however contains 100 pbw of aluminum powder.

It is again dried at 130 ° C and then calendered at 60 ° C.

• 1000 GT einer handelsüblichen 400/oigen wässrigen, alipathischen Polyurethandispersion (Viskosität bei 25° C ca. 300 mPa-s; pH-Wert 7,0 - 8,0), hergestellt nach DE-B-1 495 847, Beispiel 17
• 20 GT eines zugehörigen Vernetzungsmittels auf Basis polyfunktioneller Aziridinverbindung und
• 10 GT eines handelsüblichen nichtionogenen Verdickungsmittels auf Polyurethanbasis (500/oige wäßrige Lösung eines Umsetzungsproduktes aus 24 GT Polyethylenglykol-/ Polypropylenglykol-Monobutylether vom Molgew. ca. 10000 (Gewichtsverhältnis EO zu PO ca. 1: 1) mit 1 GT eines Adduktes von Trimethylolpropan an Tolylendiisocyanat (Molverhältnis 1: 3))

The top coat of the following composition

• 1000 pbw of a commercially available 400% aqueous, alipathic polyurethane dispersion (viscosity at 25 ° C. approx. 300 mPa-s; pH 7.0 - 8.0), produced according to DE-B-1 495 847, example 17
• 20 pbw of an associated crosslinking agent based on polyfunctional aziridine compound and
• 10 pbw of a commercially available non-ionic thickener based on polyurethane (500% aqueous solution of a reaction product of 24 pbw of polyethylene glycol / polypropylene glycol monobutyl ether with a molecular weight of about 10,000 (weight ratio EO to PO about 1: 1) with 1 pbw of an adduct of trimethylolpropane Tolylene diisocyanate (molar ratio 1: 3))

is applied using a circular doctor blade, then dried at 130 ° C and briefly condensed at 150 ° C.

• Wasserdichtheit nach DIN 53886 über 98,01 mbar
• Reißfestigkeit nach DIN 53867 -Kette 120,5 daN
• -Schuß 125,5 daN
• Weiterreißfestigkeit nach DIN 53859 "S"
• -Kette 10,4 daN
• -Schuß 11,3 daN
• Lichtechtheit(Xenonbelichtung nach DIN 5400 während
• 64 Std.; Bewertungsskala 1 bis 8) Note 8
• Der Schutzplanenstoff weist eine ganz beachtliche Wärmereflexion auf.

The advantageous properties of the protective tarpaulin fabric are summarized in the following table:

• Water tightness according to DIN 53886 over 98.01 mbar
• Tear resistance according to DIN 53867 chain 120.5 daN
• - Shot 125.5 daN
• Tear resistance according to DIN 53859 "S"
• -Chain 10.4 daN
• -Shot 11.3 daN
• Lightfastness (xenon exposure according to DIN 5400 during
• 64 hours; Evaluation scale 1 to 8) Note 8
• The protective tarpaulin has a very considerable heat reflection.

Example 2

Example 1 is repeated, but using polyester flicker instead of aluminum powder.

• 6 GT Polyacrylatverdicker (Emulsionscopolymerisat aus 81,9 GT Ethylacrylat, 2 GT N-Methylolacrylamid, 0,1 GT Butandioldiacrylat und 16 GT Acrylsäure, 28 Gew% Feststoffgehalt; neutralisiert mit Ammoniak) und
• 2. Strich 120 GT Polyesterflimmer und zusätzlich
• 6 GT obigen Verdickers.

1st line 80 GT polyester flicker and additional

• 6 pbw of polyacrylate thickener (emulsion copolymer of 81.9 pbw of ethyl acrylate, 2 pbw of N-methylolacrylamide, 0.1 pbw of butanediol diacrylate and 16 pbw of acrylic acid, 28% by weight solids; neutralized with ammonia) and
• 2nd line 120 GT polyester flicker and additional
• 6 GT thickener above.

The other conditions correspond to the information in Example 1. The positive results are obtained in the same way, with the heat reflection being somewhat improved.

Example 3

The polyester filament fabric described there in Example 1 is washed and pretreated in the manner described there.

• Für den 1. Strich
• 1000 GT einer nichtionogenen, Vernetzbaren ca. 450/oigen Polyacrylsäureesterdispersion (Emulsionspolymerisat aus 80 GT Butylacrylat, 13,5 GT Acrylnitril, 6 GT N-Methylolacrylamid und 0,5 GT Itakonsäure),
• 50 GT einer ca. 50%igen Aminoplastharzlösung (3 Teile Dimenthylolethylenharnstoff und 1 Teil Pentamethylolmelaminmethylether),
• 80 GT des im Beispiel 1 beschriebenen Imprägniermittels,
• 60 GT eines handelsüblichen Acrylat-Verdickers (siehe Beispiel 2),
• 25 GT konzentrierter Ammoniak,
• 30 GT eines handelsüblichen Härtungsmittels (Basis 2-Amino-2-methyl-propanol-1-hydrochlorid) und
• 70 GT Silberpulver (Korngröße 0,03 bis 0,06 mm).
• Für den 2. Strich
• Wie oben, aber mit
• 100 GT Silberpulver
• Für den Deckstrich

The coating is also carried out in the manner described in Example 1, but the following coating pastes and a total coating of 60 g / m ^{2 are} used:

• For the 1st stroke
• 1000 pbw of a nonionic, crosslinkable approximately 450% polyacrylate dispersion (emulsion polymer made from 80 pbw butyl acrylate, 13.5 pbw acrylonitrile, 6 pbw N-methylolacrylamide and 0.5 pbw itaconic acid),
• 50 pbw of an approx. 50% aminoplast resin solution (3 parts dimenthylolethylene urea and 1 part pentamethylol melamine methyl ether),
• 80 pbw of the impregnating agent described in Example 1,
• 60 pbw of a commercially available acrylate thickener (see example 2),
• 25 pbw of concentrated ammonia,
• 30 pbw of a commercially available curing agent (based on 2-amino-2-methyl-propanol-1-hydrochloride) and
• 70 GT silver powder (grain size 0.03 to 0.06 mm).
• For the 2nd stroke
• As above, but with
• 100 GT silver powder
• For the top coat

The top coat is produced in accordance with EP-A-41 607, Example 1.

Example 4

A light polyester fabric (130 g / m ² ) is finished in the manner described in Example 2 (total solid layer 50 g / m ² ).

The technological properties of the tarpaulin material correspond to the values obtained there.

Example 5

Example 1 is repeated, but only 2 lines are applied, in accordance with the 2nd line (now 1st line) described in Example 1 and the top line described in Example 1. The total application quantity is 45 g / m ² . The tarpaulin fabric obtained is technologically sound.

Claims (12)

1. Waterproof heat reflecting protective tarpaulin material, characterized in that the basic fabric is a possibly pretreated polyester lightweight fabric of a maximum 160 g/sq.m weight, coated on one side with at least one pigment bearing coating of a cross-linked polyacrylic acid ester and a top coating of polyurethane, preferably aliphatic polyurethane, the coatings representing a total of 25 to 80 g/sq.m.

2. Protective tarpaulin material according to Claim 1, characterized in that the basic fabric is a polyester filament fabric of 90 to 120 g/sq.m.

3. Protective tarpaulin material according to Claim 1 or 2, characterized in that the basic fabric is provided with two pigment bearing coatings of a cross-linked polyacrylic acid ester.

4. Protective tarpaulin according to one of Claims 1 to 3, characterized in that the coatings represent 30 to 50 g/sq.m.

5. Protective tarpaulin according to one of Claims 1 to 4, characterized in that the basic fabric is provided with a metallic coating of a cross-linked polyacrylic acid ester.

6. Protective tarpaulin according to Claim 5, characterized in that aluminium bronze or aluminium is envisaged as the metal.

7. Method of producing the waterproof heat reflective protective tarpaulin material according to Claim 1, characterized in that onto a possibly pretreated polyester lightweight fabric of a maximum 160 g/sq.m as the basic fabric there is applied on one side at least one layer (corresponding to one coating) by means of an aqueous pigment bearing cross-linkable polyacrylic acid ester dispersion and a cover layer of a polyurethane, preferably an aliphatic polyurethane, accompanied by the use of a conventional aid and with intermediate drying, whereby during the individual coatings only as much solid material is applied that the finished protective tarpaulin material contains on the basic fabric 25 to 80 g/sq.m of solids.

8. Method according to Claim 7, characterized in that a polyester filament fabric of 90 to 120 g/sq.m is used as the basic fabric.

9. Method according to Claim 7 or 8, characterized in that two air scraper coatings of the pigment-bearing cross-linkable polyacrylic acid ester are applied to the basic fabric.

10. Method according to one of Claims 7 to 9, characterized in that the finished protective tarpaulin material receives 30 to 50 g/sq.m of applied solids.

11. Method according to one of Claims 7 to 10, characterized in that metal-bearing cross-linkable polyacrylic acid esters are applied.

12. Method according to Claim 1, characterized in that aluminium bronze or aluminium bearing cross-linkable polyacrylic acid esters are applied.