Item including a laminated, metallized textile layer, in particular for sun protection, and method for grafting a metal layer in order to obtain said item

Abstract

The present invention provides an article, in particular for solar protection, comprising at least one metal-coating layer and a textile layer having an outside face comprising at least one polymer mixed with at least one plasticizer to form a first matrix. Advantageously, the bonding between said first matrix and the metal-coating layer is provided by an intermediate polymer layer comprising at least one coupling polymer, said coupling polymer being bonded by chemical bonds firstly to the first matrix and secondly to the metal-coating layer. The present invention also provides a method of fabricating such an article including a step of metal coating by depositing metal vapor under reduced pressure.

Claims

1. An article for solar protection, comprising at least one metal-coating layer and a textile layer having an outside face comprising at least one polymer mixed with at least one plasticizer to form a first matrix, the article being wherein the bonding between said first matrix and the metal-coating layer is provided by an intermediate polymer layer comprising at least one coupling polymer, said coupling polymer being bonded by chemical bonds firstly to the first matrix and secondly to the metal-coating layer, wherein the chemical bonds existing between the coupling polymer and the metal-coating layer are provided by means of M-OH functions carried by the intermediate layer or by O-M-O covalent bridges, where M=Al, Zr, Ti, Cr or Si.

2. The article according to claim 1, wherein the weight of the first matrix relative to the total weight of the article is greater than or equal to 50% and less than or equal to 85%, and the weight of the textile layer relative to the total weight of the article is greater than or equal to 25% and less than or equal to 50%.

3. The article according to claim 1, wherein the weight of the metal constituting the metal-coating layer relative to the total weight of the article is less than or equal to 0.5%.

4. The article according to claim 1, wherein said at least one polymer mixed with at least one plasticizer is selected from chlorinated polymers.

5. The article according to claim 1, wherein the textile layer comprises, at least on its outside face, fibers and/or yarns in which all or some of said fibers and/or yarns are each coated in a sheath formed by said first matrix.

6. The article according to claim 1, wherein the chemical bonds existing between the coupling polymer and the first matrix are covalent, hydrogen, or polar bonds.

7. The article according to claim 1, wherein the chemical bonds existing between the coupling polymer and the metal-coating layer are provided by means of M-OH functions, where M=Al, Zr, Ti, Cr or Si.

8. The article according to claim 1, wherein the chemical bonds existing between the coupling polymer and the metal-coating layer are provided by O-M-O covalent bridges, where M=Al, Zr, Ti, Cr or Si.

9. The article according to claim 1, wherein the intermediate polymer layer is a polymer selected from: polyesters, polyamides, polyurethanes, polyacrylics, polyolefins, copolyolefins, polyolefin elastomers, phenoxy resins, chlorinated polymers, epoxy resins, and mixtures thereof.

10. The article according to claim 1, wherein the textile layer comprises fibers and/or yarns selected from the following material(s): glass, ceramics, optical fibers, yarns based on metal alloys, basalt, carbon, polyesters, polyamides, aramids, polyvinyl alcohol (PVA), and mixtures thereof.

11. The article according to claim 1, wherein the metal constituting the metal-coating layer is aluminum.

12. The article according to claim 1, wherein the coupling polymer represents 0.1% to 25% by weight, of the total weight of said article.

13. The article according to claim 1, wherein the coupling polymer represents 0.5% to 7% by weight, of the total weight of said article.

14. A method of depositing a metal-coating layer on the outside face(s) of a textile layer, said outside face including at least one polymer mixed with at least one plasticizer forming a first matrix, in order to obtain an article according to claim 2, wherein the method comprises the following successive steps: a) preparing a solution or a dispersion including a coupling polymer or a mixture of coupling polymers, said polymer(s) carrying coupling functions capable of making chemical bonds between the coupling polymer and the first matrix, and coupling functions capable of making chemical bonds between the coupling polymer and the metal of the metal-coating layer, which functions may be identical or different; b) sizing at least the outside face of the textile layer that comprises the first matrix with the solution or dispersion prepared in step a); c) applying heat treatment serving in particular to fix the coupling polymer chemically to the surface of the first matrix of the textile layer so as to fix a layer of intermediate polymer on the textile layer first matrix; and d) metal coating, by depositing metal vapor under reduced pressure on at least a portion of the outside face of the previously treated textile layer, leading to the formation of chemical bonds between the intermediate polymer layer and the metal-coating layer that is formed; wherein the chemical bonds between the coupling polymer and the metal-coating layer are provided by means of M-OH functions carried by the intermediate polymer layer or by O-M-O covalent bridges, where M=Al, Zr, Ti, Cr or Si.

15. The method according to claim 14, wherein the method includes a step of chemically cleaning the first matrix, said step consisting in applying a solution or a dispersion comprising a surfactant or a mixture of surfactants on the first matrix, this cleaning step taking place prior to step b) on the non-sized first matrix, or together with step b), with the surfactant(s) then being added to the solution or the dispersion in step a).

16. The method according to claim 14, wherein the preparation in step a) is an aqueous dispersion made with 1% to 30% coupling agent(s), 50% to 95% polymer(s) with reactive functions, and 0.05% to 1% formulation agent(s), the percentages being expressed for dry extract relative to the total weight of the dry extract corresponding to the prepared dispersion.

17. The method according to claim 16, wherein the coupling agent(s) is/are selected from: silanes; titanates; zirconates; aluminates; blocked isocyanates; and organochromium complexes.

18. The method according to claim 16, wherein the coupling agent(s) is/are selected from organosilanes carrying one to three OH or alkoxy functions, and at least one organic portion R possessing a function enabling covalent grafting on the polymer with reactive functions and/or on the first matrix and/or on the metal-coating layer.

19. The article according to claim 4, wherein said at least one polymer mixed with at least one plasticizer is a polyvinyl chloride.

20. The article according to claim 1, wherein M=Si.

21. The article according to claim 1, wherein the at least one plasticizer comprises a phthalate.

Description

DETAILED DESCRIPTION OF EMBODIMENTS

(1) The following examples serve to illustrate the embodiments of the disclosure and they are given in a non-limiting manner.

EXAMPLE 1

(2) The method described below was applied to a textile layer weighing about 390 grams per square meter (g/m.sup.2), comprising yarns sheathed in a first matrix comprising polyvinyl chloride (PVC) together with at least one plasticizer, such as diisodecyl phthalate (DIDP). The textile layer comprised glass yarns representing about one-third by weight of its total weight and said first matrix represented about two-thirds by weight of its total weight. Thus, in this example, the first matrix was to be found on both of the opposite inside and outside faces of the textile layer. The plastic-coated textile layer was subjected to a prior chemical cleaning step by being immersed in a cleaning solution as described in Table 1 below. The plastic-coated textile layer as cleaned in this way is then dried by passing over a tenter frame, with the drying time being 120 seconds (s) at 150° C.

(3) TABLE-US-00001 TABLE 1 Type of raw Chemical nature Percentage by material Commercial reference weight Dispersion medium water 99.5 Surfactant Sulveol NSE 0.5 Total 100.0

(4) The preparation for deposition was prepared by adding in succession into the necessary quantity of water while being stirred: Permutex Evo Ex RU 92-605 (having a dry extract of about 40%), Permutex XR 92-203, was then BYK 094 drop by drop with the proportions set out in Table 2 below. The deposition preparation was maintained under stirring at 100 revolutions per minute (rpm) to 300 rpm using a four-blade mixer having a deflocculating type blade and at ambient temperature (20° C.-25° C.) for at least 30 minutes (min).

(5) TABLE-US-00002 TABLE 2 Type of raw Chemical nature Percentage material Commercial reference by weight Dispersion medium water 34.0 Polymer with Stahl Permutex Evo Ex 60.0 reactive functions RU 92-605 polyurethane Coupling agent Stahl Permutex XR 6.0 92-203 blocked isocyanate Anti-foaming agent BYK Chemie Byk 094 0.05 polydimethylsiloxane Total 100.05

(6) The plastic-coated and cleaned textile layer was then passed through a bath of the above-described deposition preparation (step a)), and then squeezed between to rollers in order to remove the excess deposition preparation by padding, the pressure in the padding mangle lying in the range 0.7 bar to 1.5 bar. The plastic-coated textile layer impregnated with the deposition preparation was dried on a tenter frame at 150° C. for about 120 s (step c)).

(7) The plastic-coated textile layer itself coated in the deposition preparation was then subjected to a preliminary step i) of activating the first matrix coated in the intermediate polymer layer, which consisted in introducing the plastic-coated textile layer with the intermediate polymer layer obtained at the end of step c) into an enclosure, in particular a vacuum enclosure (pressure of about 10.sup.−5 Torr) into which an oxygen plasma was injected, the temperature of the plasma gas being about 900° C.-1000° C. The treatment time was shorter than 1 s.

(8) Prior to the plasma treatment i), the plastic-coated textile layer having the intermediate polymer layer at the end of step c) was dried in a gas oven (speed 10 meters per minute (m/min)) at a temperature of about 130° C.

(9) The plastic-coated textile layer after plasma treatment was then subjected to a metal coating step (step d)) by depositing aluminum vapor under low pressure on its outside face at a pressure in the range 10.sup.−4 millibars (mbar) to 10.sup.−5 mbar, the metal coating speed lying in the range 9 meters per second (m/s) to 14 m/s.

(10) By way of example, the above-defined steps i), c), and d) can be performed using a Leybold TopMet machine, e.g. as sold by the supplier Leybold Systems.

(11) The solar protection article that was obtained presented a weight per unit area lying in the range 395 g/m.sup.2 to 400 g/m.sup.2.

(12) The OF value of the textile layer is 5% was measured in compliance with the April 2011 EN 410 standard. The Rs value of the resulting article for solar protection as measured in compliance with the April 2011 EN 410 standard was 84%.

(13) The resulting solar protection article presented an M1 fire resistance value measured in compliance with the (February 2004) NFP 92507 standard and an absolute DL* value in the adhesion test as described below (−DL* peeling) of 0.6±0.01 as measured immediately after metal coating, and of 0.6±0.01 as measured 11 months after metal coating.

(14) The method of measuring peeling strength in the present specification comprises the following steps: cutting out a strip of SU that is about 4 centimeters (cm) to 5 cm wide and about 25 cm long; positioning double-sided adhesive tape having the reference 64621 as produced by the supplier TESA on the metal-coated face of the solar protection article for testing over 20 cm, while leaving 5 cm free of tape in order to obtain to position it in the jaw of the dynamometer, and also having 5 cm free of SU; passing through a laboratory padding mangle, pressure =1 bar; dynamometer testing, traction method, travel speed=100 millimeters per minute (mm/min); positioning the SU in the bottom jaw and the free adhesive tape portion in the top jaw; selecting the “traction” method and peeling the adhesive tape from the solar protection article, with the result being the maximum resistance value; and measuring DL* in a spectrocolorimeter on the adhesive tape, measuring L* before the test and L* after the test. The greater the value of DL* (delta), the greater the amount of the metal coating that has become deposited on the adhesive tape, and conversely the closer the value of DL* is to zero, the greater the mechanical strength of the metal-coated layer.

EXAMPLE 2

(15) The above-described method was applied to a textile layer, weighing about 390 g/m.sup.2, comprising yarns sheathed in a first matrix comprising polyvinylchloride (PVC) with at least one plasticizer, such as DIDP. The first matrix is thus to be found on both of the opposite inside and outside faces of the textile layer. In this example, the deposition preparation was formulated so as to make it possible also to clean the plastic-coated textile layer chemically.

(16) The deposition preparation was prepared by adding the following in succession to the necessary quantity of water that was maintained under stirring: BYK 094; a phenoxy resin (InChemRez PKHW38); a silane (Coatosil C2287); and AMP 90 using the proportions set out in Table 3 below. The deposition preparation was maintained under stirring at 100 rpm to 300 rpm using a four-blade mixer having a deflocculating type blade at ambient temperature (20° C.-25° C.) for at least 30 min.

(17) TABLE-US-00003 TABLE 3 Type of raw Chemical nature Percentage material Commercial reference by weight Dispersion medium water 50.0 Polymer with InChemRez PKHZ38 49.3 reactive functions phenoxy resin Coupling agent Coatosil C2287 silane 0.7 (3-glycidoxypropylmethyl diethoxysilane) Anti-foaming agent BYK Chemie Byk 094 0.05 polydimethylsiloxane Surfactant Dow Amp 90 2-amino-2- 0.15 methyl-1-propanol Total 100.0

(18) The plastic-coated and cleaned textile layer was then passed through a bath of the above-described deposition preparation (step a)), and was then squeezed between two rollers in order to remove excess deposition preparation by padding, the padding mangle pressure lying in the range 0.7 bar to 1.5 bar. The plastic-coated textile layer impregnated with the deposition preparation was dried on a tenter frame at 120° C. for about 1 min (step c)).

(19) Advantageously, the deposition preparation was formulated so as also to perform chemical cleaning of the textile layer, in particular so as to degrease the textile layer, i.e. remove the plasticizer(s) migrating to the surface of the fibers and/or the yarns.

(20) The plastic-coated textile layer coated in the deposition preparation was then subjected to a preliminary step i) of activating the first matrix coated in the intermediate polymer layer, which consisted in introducing the plastic-coated textile layer including the polymer intermediate layer obtained at the end of step c) into a closed enclosure, in particular a vacuum enclosure (pressure about 10.sup.−5 Torr) into which an oxygen plasma was injected, the temperature of the plasma gas being about 900° C.-1000° C. In this particular example, this was plasma treatment. The treatment time was shorter than 1 s.

(21) Prior to the preliminary activation step i), the plastic-coated textile layer including the intermediate polymer layer at the end of step c) was dried in a gas oven (speed 10 m/min) at a temperature of about 130° C.

(22) The plastic-coated textile layer after plasma treatment was then subjected to a metal coating step (step d)) by depositing aluminum vapor under low pressure on its outside face at a pressure in the range 10.sup.−4 mbar to 10.sup.−5 mbar, the metal coating speed lying in the range 9 m/s (m/s) to 14 m/s.

(23) The resulting solar protection article had weight per unit area of about 395 g/m.sup.2 to 400 g/m.sup.2.

(24) The OF value of the textile layer was 5% as measured in compliance with the April 2011 EN 410 standard. The Rs value of the resulting article for providing solar protection as measured in compliance with the April 2011 EN 410 standard was 85%.

(25) The resulting solar protection article presented a fire resistance value M1 as measured in compliance with the (February 2004) NFP 92507 standard and an absolute DL* value in the adhesion test described below (peeling −DL*) of 0.7±0.01 immediately after metal coating, and of 0.68±0.01 as measured 11 months after metal coating.

EXAMPLE 3

(26) This example differs from Example 2 by the preparation of the deposition dispersion in step a).

(27) An epoxysilane was initially hydrolyzed under the conditions set out in Table 4 below in order to form a coupling agent. Acetic acid was added to Coatosil MP 200 under stirring at a speed of about 100 rpm to 300 rpm, at ambient temperature (20° C.-25° C.) using a four-blade mixer having a deflocculating type blade for 10 min. Thereafter, deionized water was added initially drop by drop and then at a faster rate to obtain the quantity set out in Table 1. The pH of the coupling agent was about 3.

(28) TABLE-US-00004 TABLE 4 Type of raw Chemical nature Percentage by material Commercial reference weight Dispersion medium water 60 Coupling agent Coatosil MP 200 30 epoxysilane 40% acetic acid CH.sub.3COOH 10 Total 100.0

(29) The deposition preparation was prepared by adding the following in succession to the necessary quantity of water (provided by the hydrolyzed silane) while being maintained under stirring: BYK 094; a phenoxy resin (InChemRez PKHW38); and hydrolyzed Coatosol MP 200 (cf. below) in the proportions set out in Table 5 below. The deposition preparation was maintained under stirring at 100 rpm to 300 rpm using a four-blade mixer having a deflocculating type blade, at ambient temperature (20° C.-25° C.) for at least 30 min.

(30) TABLE-US-00005 TABLE 5 Type of raw Chemical nature Percentage by material Commercial reference weight Polymer with InChemRez PKHW38 70.0 reactive functions phenoxy resin Coupling agent Hydrolyzed MP 200 30.0 as in Table 4 Anti-foaming agent BYK Chemie Byk 094 0.05 polydimethylsiloxane Total 100.05

(31) The plastic-coated and cleaned textile layer was then passed through a bath of the above-described deposition preparation (step a)), and then squeezed between two rollers in order to remove the excess deposition preparation by padding, the pressure of the padding mangle lying in the range 0.7 bar to 1.5 bar. The plastic-coated textile layer impregnated with the deposition preparation was dried on a tenter frame at 150° C. for about 2 min (step c)).

(32) The preliminary activation step i), and the metal coating step d) was applied to the textile layer impregnated with the deposition solution and dried as defined in Example 2.

(33) The Rs value was 83.7% measured in compliance with the April 2011 EN 410 standard.

(34) The resulting solar protection article had a weight per unit area of about 395 g/m.sup.2 to 400 g/m.sup.2.

(35) The resulting solar protection article presented a fire resistance value M1 in compliance with the (February 2004) NFP 92507 standard and an absolute value of DL* in the above-described adhesion test (peeling) of 0.65 ±0.01 immediately after metal coating, and of 0.64 ±0.01 measured 11 months after metal coating.

EXAMPLE 4

(36) This example differs from Example 2 by the components of the deposition preparation in step a). Given that the coupling polymer in this specific example was formed from the coupling agent alone, the proportion by weight of coupling agent was much greater than the proportion by weight used as coupling agent compared with the dry extract in the examples that also made use of a polymer with reaction functions.

(37) TABLE-US-00006 TABLE 6 Percentage Type of raw Chemical nature by material Commercial reference weight Dispersion medium water 70 Coupling agent Coatosil C2287 30 Anti-foaming agent BYK Chemie Byk 094 0.05 polydimethylsiloxane Surfactant Dow Amp 90 2-amino-2- 0.15 methyl-1-propanol Total 100.0

(38) The Rs value as measured on the finished article (395 g/m.sup.2-400 g/m.sup.2) was 83.7% measured in compliance with the April 2011 EN 410 standard.

(39) The resulting solar protection article presented a fire resistance value M1 as measured in compliance with the (February 2004) NFP 92507 standard and an absolute value of DL* in the above-described adhesion test (peeling) of 0.65±0.01 immediately after metal coating, likewise of 0.65±0.01 three months after metal coating, and still of 0.64±0.01 six months after metal coating.

COMPARATIVE EXAMPLE 5

(40) A plastic-coated textile layer was subjected to all of steps defined in Example 1, with the exception of the steps serving to apply an intermediate polymer layer (steps a), b), and c)).

(41) The resulting solar protection article presented a fire resistance value M1 measured in compliance with the (February 2004) NFP 92507 standard and a value in the adhesion test described below (peeling -DL*) of 2 immediately after metal coating. After six months, the absolute value of DL* rose to 3. Peeling strength thus decreased strongly, with this drop being due very probably to the plasticizer migrating to the interface between the first matrix and the metal-coated layer.

(42) By way of comparison, after six months, the absolute value of DL* in Examples 1 to 3 of the disclosure lay in the range 0.4 to 0.6. Peeling strength was thus much more stable and durable independently of migration of the plasticizer.

(43) Examples 6 and 7 below were performed using the same steps and on the same plastic-coated textile layer as defined with reference to Example 1, with only the different characteristics being set out in Table 7 below.

(44) TABLE-US-00007 TABLE 7 Comparative CAS No. or Component Order of example 6 Example 7 generic name function insertion (C) (D) Water Solvent 1 50 g 50 g Polysiloxane Anti-foaming 2  1 g  1 g agent Carboxyl Binder 3 50 g 50 g acrylic acid polymer with ester reactive copolymer functions 28897-60-1 Epoxysilane 4 — 0.7 g  coupling agent 67674-67-3 Surfactant 5  1 g  1 g Stirrer IKA small Dispermat blade small blade Stirring rpm 600 600 speed Padding bar 1 1 pressure 1st pass ° C. 135° C. 135° C. drying Drying time min 2 2 pH - T0 8.75 pH - T48 h 8.90 Rs (%) 84.8 8.48 measured with April 2011 EN 410 standard Absolute value of DL* in below- 1.39 ± 0.01 0.38 ± 0.01 described adhesion test (peeling- DL*) immediately after metal coating Absolute value of DL* in below- 1.43 ± 0.01 0.37 ± 0.01 described adhesion test (peeling- DL*) two months after metal coating

(45) The articles of Examples 6 and 7 were coated in a varnish on the metal-coated face in order to avoid the metal-coating layer oxidizing. The dispersion forming the varnish is set out in Table 8 below.

(46) TABLE-US-00008 TABLE 8 % by weight relative to the total Component Order of weight of the Components function insertion dispersion Water Solvent 1 90 Dispersion of Binder 2 10 fluorocarbon resin Polysiloxane Anti-foaming 3 0.1 agent

(47) It can be seen that Example 7 provides very good peeling strength compared with comparative Example 6.

(48) The peeling strength in comparative Example 6 as obtained without coupling agent deteriorates over time as a result of the plasticizer migrating.

(49) The use of a coupling polymer that develops chemical bonds with the first matrix and with the metal-coating layer serves to greatly improve the peeling strength as measured immediately after metal coating. This peeling strength advantageously remains stable after six months, as shown above.

(50) It should be observed that the peeling strength of comparative Example 6 is improved compared with comparative Example 5 because of the presence of an adhesive layer that is formed specifically by the binder and because of the step of chemically cleaning the plastic-coated textile layer.

(51) Notably, although some features, concepts or aspects of the inventions may be described herein as being a preferred or advantageous arrangement or method, such description is not intended to suggest that such feature is required or necessary unless expressly so stated.