WO2022180442A1

WO2022180442A1 - Multi-layer composite material with cold effect

Info

Publication number: WO2022180442A1
Application number: PCT/IB2021/057066
Authority: WO
Inventors: John Jairo ÁLVAREZ; Dadmar Magaly FUENTES VELASQUEZ; Myzenth JANSEN MENDEZ; Juliana Lasprilla Botero; Jorge Ricardo SANTANA CASTILLO
Original assignee: Proquinal
Priority date: 2021-02-26
Filing date: 2021-08-02
Publication date: 2022-09-01
Also published as: CO2021002728A1

Abstract

A multi-layer compound material comprising a lower textile component, a bonding layer and a multi-layer upper layer. Where the multi-layer upper layer comprises a foamed or non-foamed lower layer, a compact intermediate layer with cold pigments and a protective external coating layer. The product obtained is characterised in that it is the complement between design and comfort for materials that require a surface with a good finish and high durability; this enables the use of a wide range of dark shades and colours outdoors and in environments with high solar radiation. The structure of this material enables a reduction in the amount of radiant energy or heat absorbed by this type of material, causing even dark surfaces to feel much cooler to the touch, reducing the temperature by between 15º and 20º when compared with conventional materials.

Description

MULTILAYER COMPOSITE MATERIAL WITH COLD EFFECT

FIELD OF THE INVENTION

The development is aimed at the production of multilayer composite materials such as synthetic materials. Particularly, in the production of coated textile materials for seat upholstery, for example, automobile, motorcycle or yacht seats, furniture, and vehicle interior trim or yacht panels.

DESCRIPTION OF THE STATE OF THE ART

The energy emitted by the sun interacts with materials in various ways. Some materials (for example, opaque materials) can absorb energy in the visible light range of the electromagnetic spectrum and subsequently emit it in the infrared, that is, in the form of heat, while other materials can accumulate energy in the infrared, causing both cases an increase in the temperature of the material. So the energy absorbed or stored and subsequently emitted as heat by the surface of a material is determined by the degree of absorption and reflection of light. Therefore, depending on the color, some materials absorb or store more energy and can get hotter. Dark-colored surfaces generally get hotter than light-colored surfaces when exposed to sunlight, and as a result, light-colored surfaces feel more “cool” or “cooler” to the touch compared to dark surfaces. This effect is clearly seen, for example, in white or light-colored roofs whose surface allows sunlight to be reflected more efficiently, avoiding sudden changes in temperature inside the buildings, allowing houses with lower ceilings to be built.

Similarly, light colored coated textile materials absorb less solar energy, heat up less and, therefore, provide a cool sensation to the touch, facilitating their use outdoors or in environments with high solar radiation. However, this phenomenon has limited the use of dark-colored coated textile materials in this type of environmental conditions because, when heated, they produce an unpleasant sensation to the touch and even, in extreme conditions, they could produce burns to the user's skin. In addition, since the temperature rise of the material can be very high, the integrity of the material can be compromised, altering its performance and reducing its useful life. To overcome these problems, in particular to reduce the degree of heating of dark-colored textile materials to be used outdoors or in environments with high solar radiation, some multilayer composite materials have been developed whose architecture makes it possible to reduce the heating of the material and provide a cooler sensation to the touch.

For example, US20100009146 discloses an infrared radiation reflective artificial leather-like material comprising (a) a surface layer of a polyvinyl chloride resin, a mixture of black pigments (perylene black and carbon black) and a plasticizer; (b) a foam layer comprising a white titanium dioxide pigment, a polyvinyl chloride resin and a plasticizer and (c) a substrate layer comprising a polyester fiber textile and a white titanium dioxide pigment . In particular, since the surface layer reflects visible light, but transmits infrared radiation causing the material to heat up, this document proposes a mixture between perylene black and carbon black, so that perylene black (which actually has a greenish tone) absorbs a smaller amount of energy and therefore avoids excessive heating of the material, while the black carbon (always placed in less quantity) fully expresses the black tone of the material.

Additionally, there are some commercial alternatives such as Skai® cool colors PLUS, which describes a coating film for exterior use characterized by a three-layer structure equipped with cool color technology (cold pigments) that ensures much less heating under sunlight. direct. These commercial materials promise to reduce heat absorption especially on dark surfaces.

On the other hand, several multilayer composite materials have been designed whose characteristics provide different functionalities, including the possibility of being used outdoors. For example, US20190009508 discloses a coating film in the form of layers or tiles. Particularly, it discloses a process for coating a textile backing layer, wherein the coating film has a multilayer top layer and a tie layer having multiple layers for bonding to the textile backing layer, wherein the polyurethane tie layer has thermoplastic properties and a thickness between 0.080nm and 0.500mm and is bonded to the top layer. The multilayer top layer is also a polyurethane layer and has one to two layers, with an outer layer and an inner layer, does not have thermoplastic properties, and has an amorphous or predominantly amorphous structure. Also, the multilayer top layer is thinner than the tie layer.

For its part, US20180072027 discloses a multilayer composite material comprising a layer of textile material; optionally at least one tie layer; a polyurethane layer with capillaries passing through the entire thickness of the polyurethane layer, wherein the textile material layer and the polyurethane layer are bonded to each other directly or by means of a bonding layer. Where the layer of textile material is in direct contact with the first layer of polyurethane, which in turn is in direct contact with the second layer of polyurethane. The second polyurethane layer and the textile material are the outer surfaces of the multilayer textile composite material. The outer surface of the second layer of polyurethane is patterned with small polyurethane hairs. The second polyurethane layer also has capillaries.

However, although these multilayer composite materials are useful for many applications, in some others they have insufficient performance to meet the most demanding requirements. In particular, many of the materials developed so far do not provide a cool touch effect and if they do, the degree of heating of the material is still too high or not fully demonstrated. In addition, these materials do not allow the development of a wide range of colors and shades, both light and dark, and they are not very versatile in providing different possibilities of surface textures, so there is still a need to develop multilayer composite materials such as textile materials capable of to provide an effective cold touch effect with different colours, shades and textures.

Therefore, the present development proposes a new alternative for coated textile materials, mainly in dark colors, which corresponds to a multilayer composite material useful outdoors or in environments with high solar radiation with the ability to provide a cool effect to the touch due to to a lower absorption and accumulation of solar radiation, which generates a lower surface temperature compared to a conventional material. The technical effects achieved with the composite material multilayer of the present development are achieved thanks to its structure (order and composition of the layers) and the microstructure and specific formulation of the pigments used. The technical characteristics of this development also allow a wide range of colors, tones and textures to be obtained without sacrificing the material's performance against radiation. Including, the material of the present development can also be overprinted without affecting the thermal performance in no more than between 5 °C and 10 °C.

BRIEF DESCRIPTION OF THE INVENTION

The present development is directed to a multilayer composite material comprising a textile component, a multilayer layer, and a tie layer between the multilayer layer and the textile component. Wherein the multi-layer top layer comprises a bottom layer, an intermediate layer compacted with cold pigments and a protective outer coating layer.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 describes an embodiment of the structure of the multilayer composite material according to what is described in Examples 1, 2, 4 to 7. Where the material composed of a lower textile component (1), a bonding layer (2) and a multilayer upper layer (3) comprising a foamed or non-foamed lower layer (4); a compact intermediate layer of cold pigments (5) and a protective coating layer (6).

FIG. 2 describes an embodiment of the structure of the multilayer composite material according to what is described in Example 3, composed of a lower textile component (1), a bonding layer (2) and an upper multilayer layer (3) comprising a lower layer foamed or non-foamed (4); a compact intermediate layer of cold pigments (5); a protective coating layer (6) and an embossing layer (7).

FIG. 3 shows the thermal behavior of two multilayer materials where the cold pigments were processed in two different ways. The short dotted line represents a material in which the cold pigments were processed in a mill of spheres (7170) while the solid line represents a material in which the cold pigments were processed with a three-cylinder mill (7871).

FIG. 4 shows the thermal behavior of a black multilayer composite material of the present development (#8711) compared with a commercial reference material that claims to have a cold effect and with a conventional material. The continuous line represents the thermal behavior of the material of the present development, the dotted line cuts the behavior of the conventional material and the long dotted line represents the behavior of the commercial reference material with cold effect.

FIG. 5 shows the thermal behavior of a multilayer material like the one of the present invention (#26948) and a commercial reference material that declares to have a thermal effect. The continuous line represents the commercial reference material and the short dotted line represents the multilayer composite material of the present development.

FIG. 6 shows the heating and cooling thermogram of a multilayer material like the one of the present invention (#26948) and a commercial reference material that claims to have a thermal effect. The continuous line represents the commercial reference material and the short dotted line represents the multilayer composite material of the present development.

FIG. 7 shows the effect of a stamping layer on the thermal behavior of the multilayer materials of the present development. The solid line represents the thermal behavior of a conventional material, the short dotted line represents a multilayer composite material with an embossing layer and the long dotted line represents the thermal behavior of a multilayer material without the embossing layer.

DETAILED DESCRIPTION

The development is aimed at multilayer composite materials such as textile materials for coated fabrics which allow these materials to heat up between 20% and 30% less than conventional materials under exposure to solar radiation. In particular, the development is aimed at a multilayer composite material that It comprises a lower textile component, a bonding layer and a multi-layered upper layer.

For example, a conventional coated textile material in black color reaches a temperature of up to 78 °C after being exposed for 20 min to an intensity of infrared radiation of 250 W (following the ASTM D4803-10 standard), while the material of the present development in the same color reaches a temperature of up to 58 °C under the same test conditions.

For purposes of the present invention, composite material is understood as multiphase materials formed by the combination of two or more chemically and physically different materials or phases. The combination of materials or phases gives the resulting material the joint characteristics of its components, so that specific properties are obtained that the starting materials do not have. Consequently, the characteristics and properties of composite materials depend on the characteristics of the starting materials and their arrangement (organization) in the composite material.

As for the term "multilayer" it refers to a composite material that has two or more layers where each of the layers has different structural characteristics, for example, in terms of components or properties. The multilayer composite material has the physical, mechanical and aesthetic characteristics of all the layers of which it is composed.

For the purposes of this development, "cold effect" is understood as the sensation perceived to the touch of a surface, generated by the reduction in temperature reached by a material when exposed to a source of radiation, including solar radiation and thermal radiation, as a result less absorption and accumulation of said radiation sources.

The developed multilayer composite material comprises: a lower textile component (1); a tie layer (2); a multilayer top layer (3); wherein the lower textile component and the upper multi-layer layer are bonded together by the tie layer; wherein the multilayer upper layer comprises: a lower layer (4); a compact intermediate layer with cold pigments (5); and a protective outer coating layer (6); and optionally a print layer (7) located between the compact intermediate layer with cold pigments and the outer layer of protective coating.

The lower textile component (1) works as a support, contributing to the mechanical resistance including tension, tearing, elongation and comfort of the material. The lower textile component can be a fabric of natural origin, synthetic or a mixture thereof. When the lower textile component is of synthetic origin, it is selected, but not limited, from polyester, recycled polyester, nylon, fiberglass, elastane, biopolymers or mixtures thereof. When the lower textile component is of natural origin, it is selected, but not limited to yarns from natural sources, cotton, recycled cotton, bamboo, linen, viscose, coconut fiber, pineapple fiber, wool, or mixtures of the above. It is even possible that, in some embodiments, the lower textile component is a polyester-cotton, polyester-fiberglass, polyester-elastane blend. In a preferred embodiment the lower textile component is 100% polyester, 90% polyester or 80% polyester.

A bonding layer (2) is located on the lower textile component layer. The bonding layer functions as a bonding agent that allows the textile component layer and the multi-layer top layer to be held together. The bonding layer has a polymer base and at least one additive. Possible polymer bases are selected from, but are not limited to, polyurethane, acrylic, and polyvinyl chloride (PVC). Additives are selected from, but are not limited to, plasticizers (primary or secondary), stabilizers, antimicrobial agents, flame retardants, rheology modifiers, mineral fillers, and catalysts. In one embodiment, the tie layer comprises PVC, primary plasticizers, secondary plasticizers, flame retardants, mineral fillers, and antimicrobial agents. In another embodiment, the tie layer comprises PVC, a mineral filler, a primary plasticizer, a secondary plasticizer, a thermal stabilizer, and a microbial agent. The multilayer upper layer (3) provides the comfort and aesthetics of the material. The multilayer top layer allows materials to be obtained with different types of finishes, modifying characteristics such as tonality, stamping, textures and sensation to the touch. Likewise, the multilayer top layer provides resistance to the material against aging and/or degradation due to thermal, chemical effects or physical wear due to abrasion. The multilayer top layer comprises a foamed or non-foamed bottom layer (4), a compact intermediate layer (5) with cold pigments, and a protective outer coating layer (6).

In one embodiment of the present development, the bond between the three layers of the multilayer top layer is achieved by thermopressure melting processes, taking advantage of the thermoplastic properties of the components of these layers. In another embodiment, in case said layers are not fused by thermopressure methods (for example, when the materials do not have thermoplastic properties), it is necessary to incorporate a bonding system. Said bonding system is selected from, but not limited to, thermoplastic polymers, thermosetting polymers and elastomers, and optionally additives such as Theological agents, tackifying resins, solvents and catalysts are added.

The lower layer (4) has the function of contributing to the comfort of the material, giving it thickness and generating a sensation of padding and softness. In addition, it helps in the performance of the material, for example, making it more resistant to fire. The lower layer is characterized in that it can be a non-foamed (compact) or foamed polymeric film with closed and flexible cells, with the ability to insulate and dissipate heat. In one embodiment, the lower layer comprises a foamed polymeric base selected from polyvinyl chloride, silicone, polyurethane, thermoplastic elastomers, a pigment, and at least one additive including swelling agents responsible for producing the material in foam form. In a preferred embodiment the polymeric base is polyvinyl chloride. For the purposes of this development, swelling agents are understood as substances that allow the generation of gases, for example, carbon dioxide, nitrogen or ammonium, which when mixed with polyvinyl chloride create bubbles and reduce the density of the layer. The bottom layer optionally has additives including, but not limited to plasticizers, stabilizers, antimicrobial agents, or Theology modifiers. Optionally the lower plastic layer can also understand cold pigments of the NIR system (near-infrared spectral region). Additionally, in another embodiment of the invention, the lower layer may be non-foamed and may also contain cold pigments.

For purposes of the present invention, it is understood that the "cold pigments of the NIR system" comprise an inorganic complex of compounds of metallic origin, with the ability to reflect much of the heat that is generated under sun exposure, thanks to its characteristics. , chemical, optical, physical and microstructural. Some examples of cold pigments are selected from, but not limited to, anatase-type titanium dioxide (ΉO ₂ ), di-iron trioxide (FciOfl. spinel cobalt blue aluminum (C0AI ₂ O ₄ ), iron oxide and chromium (CnOfi. cobalt and titanium green spinel (C0 ₂ T1O ₄ ), rutile type titanium dioxide (ΉO ₂ ), antimony and manganese, and mixtures thereof in different proportions according to the desired color and tone including variations of natural occurrence or those obtained through artificial synthesis processes.In this regard, it is important to point out that there is a wide range of this type of pigments available that could also be used in the materials of this development.

A compact intermediate layer with cold pigments (5) provides part of the appearance by providing the color and hue of the material. In addition, it contributes to the resistance to wear generated by exposure to solar radiation, environmental conditions and abrasion wear. The intermediate layer with cold pigments is characterized in that it comprises a polymeric base, plasticizers, cold pigments of the NIR system and at least one additive. In a preferred embodiment, the polymer base of the cold-pigmented interlayer is polyvinyl chloride. In a preferred embodiment, the cold pigments are of the NIR system. Among the additives that this layer may include are, but are not limited to, plasticizers, fillers, antimicrobial agents, stabilizers, mineral fillers, rheology modifiers and flame retardant agents. In one embodiment of the invention, the cold pigment compact intermediate layer comprises polyvinyl chloride, plasticizers, thermal stabilizers, UV stabilizers, mineral fillers and antimicrobial agents.

The cold pigments may or may not be carriers. In the event that the cold pigments are conveyed, they can be conveyed in a plasticizer, a resin plasticized or in a polymeric compound (Master batch). For example, it can be added in an extrusion or plastisol system. So that the pigments in solid form can be well wetted and incorporated into the polyvinyl chloride plastisol, it is sometimes necessary to carry out a grinding process that must be done carefully (controlling conditions such as time, grinding mechanism, number of grinding passes and internal pressure in the mill) to disaggregate the pigment particles without affecting the shape, size and individual microstructure of the cold pigments. Any unwanted alteration of the cold pigments could irremediably modify the microstructural characteristics, reducing or even eliminating the ability of the pigment to reflect infrared radiation, and as a consequence, negatively affect the efficiency of the material against exposure to solar radiation.

For example, when comparing the grinding performed by a sphere system versus a three-cylinder system, the inventors identified that the sphere system exerts a very aggressive force and destroys the pigment particle, affecting its microstructure to the point of completely damaging the reduction efficiency. temperature of the pigment and, consequently, the developed materials did not present the best performances. In comparison, the three-cylinder system performs a more regulated mechanical work, which allows the disaggregation of the particles without modifying the size or microstructure of the pigments, so its optical performance or temperature reduction was not affected.

A protective outer coating layer (6) that contributes to reducing the stickiness that can be generated on the surface of the multilayer layer, modifying the surface characteristics related to the sensation to the touch such as non-slip, waxy, anti-scratch effects , among others. It also provides resistance to abrasion, chemical treatments (resistance to cleaners and stains), fat extraction and antimicrobial properties. The protective outer coating layer is characterized in that it comprises a polymeric system conveyed in water or an organic solvent system with at least one catalyst. The protective outer coating layer comprises a polymeric base, at least one copolymer and optionally an additive. The polymer base can be an acrylic or polyurethane polymer. The copolymer is selected from, but is not limited to, vinyl polymers, polyurethane or acrylics. Possible outer coating protective layer additives include, but are not limited to, catalysts, defoamers, feel modifiers, matting agents, viscosity regulators, and antimicrobial agents.

In an embodiment such as the one shown in FIG. 2, the multilayer top layer additionally has an embossing layer (7). Said printing layer is located between the compact intermediate layer with cold pigments and the outer layer of protective coating. The print layer comprises at least one polymeric resin, a copolymer, at least one solvent and pigments. The polymeric resin may be an aerifying resin. The copolymer is selected from, but is not limited to, vinyl, polyurethane, or acrylic polymers. Solvents are selected from, but are not limited to, water, organic and inorganic solvents. In particular, the pigments used in the printing layer are organic and have a high color-providing property (maximum of 60% of inks in formulations), are lightfast (pass Xenotest, QUV 650 hours, SAEJ 1885 , and ISO 105:B04) and easy to dissolve (in solvents such as: MEK, toluol, isobutyl acetate and butyrate acetate).

The process to put the stamping layer can be done by means of an applicator roller, screen printing, direct printing or transfer, among others.

In one embodiment, the multilayer composite material comprising: a lower textile component that is polyester; a tie layer comprising polyvinyl chloride, plasticizers, heat stabilizers, mineral fillers, and antimicrobial agents; a foamed or non-foamed bottom layer comprising polyvinyl chloride, plasticizers, heat stabilizers, mineral fillers, antimicrobial agents, swelling agents (if foamed), and at least one pigment; a compact intermediate layer with cold pigments comprising polyvinyl chloride, plasticizers, UV light stabilizers, thermal stabilizers, mineral fillers, NIR system cold pigments and antimicrobial agents; and an outer layer of protective lacquer coating comprising a polymeric base dispersed either in aqueous or solvent base and at least one catalyst. The additives are selected from the lists below or any other known to a person of ordinary skill in the art. Additives are optional unless explicitly stated otherwise in each of the layers.

Plasticizers fulfill the function of giving softness and flexibility to hard polymers. These can be classified as primary plasticizers based on high molecular weight orthophthalates, trimellitate-based, adipate-based, polyester-based; or as secondary plasticizers, among which are, but are not limited to, plasticizers derived from hydrolyzed vegetable oils, pentanediol derivatives, terephthalate mixtures, paraffin derivatives.

Thermal stabilizers protect polymers from the high temperatures to which they are subjected during the different transformation processes (for example, mixing, extrusion, injection, baking, etc.) and during exposure to solar radiation during use, thus avoiding degradation of the physicochemical properties of the polymer. Thermal stabilizers include, but are not limited to metal, organic, tin, calcium and zinc stearate stabilizers.

Mineral loads or "fillers" are usually defined as insoluble materials that are normally in powder form and are used to increase volume, obtain or increase certain technical properties and/or modify optical properties. These materials can give many characteristics to the system they are in depending on whether they are active or inactive. Fillers include, but are not limited to, calcium carbonate, dolomite, soda ash, talc, silica, wollastonite, clay, calcium sulfate fibers, mica, glass beads, and alumina trihydrate.

Flame retardants are defined as a variety of additives that are added to polymeric materials to prevent fires or slow the spread of fire through them and provide additional escape time. Flame retardants include, but are not limited to, antimony trioxide, zinc borate, aluminum hydroxide, halogens, phosphorous, metal hydrates, and melamine cyanides. Antimicrobial agents are defined as additives that kill microorganisms, stop their growth, hinder or inhibit their reproduction. Microbial agents include, but are not limited to, oxybisphenoxyarsine derivatives, isothiazolone derivatives, halogen and zinc compounds, nanoparticles or silver and/or copper ions, and imidazole salts.

Swelling agents or also known as foaming agents, are a type of additives for plastics that seek to produce cellular structures, that is, structures that contain portions of fine cells filled with gas. Thus, changes in density, thermal conductivity and dissipation of acoustic and mechanical energy can be achieved. Blowing agents include, but are not limited to azodicarbonamide, zinc oxide, zinc octoate, potassium/zinc accelerator.

Defoamers are surface-active agents that act by means of intermediate surface tensions to destabilize the lacquers and release the air trapped in their mixture. Within these types of defoamers are organic defoamers (based on mineral oils) that provide excellent performance and are low cost; silicone defoamers that are highly effective at low dosage levels and finally molecular defoamers that offer excellent compatibility with most systems.

Rheology modifying agents are defined as additives for plastics that are used to modify the viscosity and improve the processability of polymers during their transformation. Rheology modifying agents include, but are not limited to, silica, pyrrolidone derivatives, epoxidized oils, and surfactants.

Pigments are used to modify the appearance of polymers for decorative purposes. They are materials that change the color of the light they reflect or transmit as a result of the selective absorption of light according to its wavelength (which is the determining parameter of color). The pigments may be independently selected from, but not limited to, organic pigments, inorganic pigments, solvent-based pigment preparations, solid pigments, and effect pigments. Some examples thereof are titanium dioxide, iron oxides, organic or inorganic. Surface modifiers or also known as touch modifiers are additive components that allow the development of formulations for coatings that improve and protect the appearance at the interface between the coating or ink and the exterior. Feel-modifying agents include, but are not limited to, silica, wax dispersions, wax emulsions, and micronized wax.

Catalysts are substances that favor or accelerate a chemical reaction without intervening directly in it, at the end of the reaction the catalyst remains unchanged. The most used catalysts are those made of platinum, palladium and vanadium or copper and nickel oxides.

The multilayer composite material as described above is characterized in that it has a tensile strength between min 121 LbL (warp) and 72 Lbf (weft), an average elongation at break of 67% (warp) and 159% ( weft), a minimum stitch resistance of 12 Lbf (warp) and 8.6 Lbf (weft), a minimum Wyzenbeek abrasion of 150,000 cycles without showing wear on the surface, a light fastness rating greater than 4 without showing significant changes , an HBU (Heat Build Up Index) between 58 °C and 61 °C in products without printing. Additionally, when subjected to an outdoor exposure test (Qlab Llorida Test) it shows no significant changes for up to 180 days of exposure.

Among the applications for multilayer materials are: upholstery for home furniture (exterior and interior); upholstery and interior and exterior panels for yachts, cars and motorcycles; development of waterproof products and awnings.

The multilayer composite material can be obtained through the manufacturing processes of coated fabrics such as: extrusion and calendering, coating transfer, baking and lamination.

It should be understood that the present invention is not limited to the modalities described and illustrated below, since as will be evident to a person skilled in the art, there are possible variations and modifications that do not deviate from the spirit of the invention, defined by the claims. EXAMPLES

Example 1. Multilayer composite material with flexible foamed PVC on a laboratory scale (FIG. 1)

Lower textile component (1): 100% polyester.

Tie Layer (2): PVC, DOTP and Chlorinated Paraffin, Tin-Based Thermal Stabilizer, Calcium Carbonate, Silica, Isothiazolone Derivative.

Multi-layer top layer (3):

A lower foamed layer (4): PVC, DOTP and chlorinated paraffin, tin carboxylate, zinc octoate, calcium carbonate azodicarbonamide, isothiazolone derivative, white pigment.

Compact intermediate layer with cold pigments (5): PVC, DOTP, benzotriazole, tin carboxylate, calcium carbonate, NIR system pigments, isothiazolone derivative, silica.

Outer layer of protective coating (6): SRT system lacquer (urea formaldehyde, toluene sulfonic acid, and aerifies (methacrylate, polyvinyl chloroacetate, solvents).

On a transfer paper, the compact intermediate layer was applied with cold pigments at a height of 0.21-0.22 mm and pre-dried at 180 °C for 20 s. Subsequently, on the compact intermediate layer with cold pigments, a foamed lower layer was applied at a height of 0.37 mm and pre-dried at 180 °C for 5 s. After the foamed bottom layer was applied, the tie layer, calibrated at 0.43 mm, was applied. Finally, the binding layer was attached to the lower textile layer to enter the oven at 200 °C for 50 s.

After the material with the cold pigment compacted middle layer, foamed bottom layer, tie layer, and bottom textile layer had dried, the transfer paper was removed to apply the protective outer coating layer to the exposed face of the layer. intermediate compact with cold pigments. Example 2. Multilayer composite material with flexible PVC on an industrial scale (F1G.

1)

It was carried out following a methodology similar to that described in Example 1, where two additional applications were made. In the first, an outer layer of protective coating based on acrylic resin dispersed in solvents and a copolymer was applied by means of application rollers over the entire PVC-coated fabric. Subsequently, the PVC-coated fabric and the outer layer of acrylic resin-based protective coating were dried at a temperature between 140 °C and 160 °C and at a speed of 16 m/min.

Then, a polyurethane base and a catalyst dispersed in formaldehyde were applied, by means of application rollers, at a temperature between 140 °C and 160 °C and at a speed of 16 m/min. The mechanical, abrasion and cleanability characteristics of the material obtained are presented in Table 1.

Table 1. Mechanical, abrasion and cleanability characteristics of the material obtained from Example 2

Test Units Value

Tensile strength LbF 121 (warp); 72 (weft) Elongation at break % 67 (warp); 159 (weft) Stitch strength LbF 12 (warp); 8.6 (screen) Wyzenbeek abrasion # cycles 100,000 cycles (no significant change)

Light fastness QUV 650 hours No significant change in color

Weather o meter 1000 hours No significant change in color (grayscale)

HBU (heat builup) (ASTM °C 59 D4803-10)

Air exposure test 180 days No significant changes Free (ASTM G47)

Example 3. Printed multilayer composite material on an industrial scale (F1G. 2) It was carried out following the methodology described in Example 1, where a printing layer was additionally applied on the intermediate layer of cold pigments (5). For the printing layer (7), an acrylic resin, a copolymer, solvents and pigments for the preparation of lacquers and inks were applied by means of an applicator roller on the entire PVC-coated fabric and a pre-drying of the surface was carried out. fabric coated with hot air at a temperature between 70 °C and 80 °C at a speed of 22 m/min. Subsequently, the outer layer of protective coating (6) was applied, which consisted of a polyurethane base and at least one catalyst dispersed in water, by means of application rollers on the entire PVC-coated fabric and the fabric was dried. coated at a temperature of 170 °C and at a speed of 22 m/min.

Example 4. Compact multilayer composite material (non-foamed)

Lower textile component (1): 100% polyester.

Bond Layer (2): PVC, DOTP and Chlorinated Paraffin, Calcium Carbonate, Silica.

Multi-layer top layer (3):

A non-foamed lower layer with cold pigments (4): PVC, DOTP, barium-zinc type thermal stabilizer, epoxidized oil, aliphatic solvent, calcium carbonate, NIR system pigments.

Compact intermediate layer with cold pigments (5): PVC, DOTP, benzotriazole, tin carboxylate, calcium carbonate, NIR system pigments.

Exterior coating protective layer (6): vinyl-acrylic system lacquer (acrylic resin, PVC, solvents).

On a transfer paper, the protective layer of the outer coating was applied by means of an applicator roller over the entire paper and drying was carried out at a temperature of 110 °C for 20 s; Subsequently, on the protective outer coating layer, the compact intermediate layer with cold pigments was applied at a height of 0.21-0.22 mm and pre-dried at a temperature of 180 °C for 20 s. Then, on the compact intermediate layer with cold pigments, the non-foamed lower layer with cold pigments was applied at a height of 0.39 mm and pre-dried at a temperature of 180°C for 15 s. Once the layers were pre-dried, the tie layer was applied, calibrated to a thickness of 0.57 mm. Finally, the binding layer was joined with the lower textile component, and the material was placed in the oven at a temperature of 200 °C for 60 s. One time drying all the material with the intermediate and lower layers with cold pigments and the textile layer, the transfer paper was removed.

Example 5. Compact multilayer PVC composite material with high fire resistance (FIG. 1)

Lower textile component (1): polyester-fiberglass blend.

Bond Layer (2): PVC, DOTP and Chlorinated Paraffin, Calcium Carbonate, Antimony Trioxide, Aluminum Hydroxide, Silica.

Multi-layer top layer (3):

Non-foamed lower layer with cold pigments (4): PVC, DOTP, triaryl phosphate, tin carboxylate, aliphatic solvent, calcium carbonate, aluminum hydroxide, zinc borate, antimony trioxide, NIR system pigments.

Intermediate layer with cold pigments (5): PVC, DOTP, benzotriazole, tin carboxylate, calcium carbonate, mixture of FR salts, NIR system pigments.

On a transfer paper, the outer layer of protective coating was applied, by means of an applicator roller over the entire paper, then drying was carried out at a temperature of 110 °C for 20 s. Subsequently, on the outer layer of protective coating, the compact intermediate layer with cold pigments was applied at a height of 0.21-0.22 mm and pre-dried at a temperature of 180 °C for 20 s. On this compact intermediate layer with cold pigments, the non-foamed lower layer with cold pigments was applied at a height of 0.42 mm and pre-dried at a temperature of 180 °C for 5 s. Once both layers had pre-dried, the tie layer was applied, calibrated at 0.6 mm. Finally, the bonding layer was joined with the textile layer and it was taken to the oven at a temperature of 200 °C for 60 s to subsequently remove the transfer paper.

Example 6. Flexible PVC multilayer composite material with a lower textile component with a mixture of polyester and cotton yarns (FIG. 1)

Lower textile component (1): 65% polyester/35% cotton Tie Layer (2): PVC, DOTP and Chlorinated Paraffin, Aluminum Hydroxide, Antimony Trioxide, Calcium Carbonate, Silica, Isothiazolone Derivative.

Multi-layer top layer (3):

A foamed bottom layer (4): PVC, DOTP, Chlorinated Paraffin, Triaryl Phosphate, Tin Carboxylate Epoxidized Oil, Zinc Octaate, Azodicarbonamide, Calcium Carbonate, Zinc Borate, Aluminum Hydroxide, Zinc Oxide, Isothiazolone Derivative , titanium dioxide.

Compact intermediate layer with cold pigments (5): PVC, DOTP, chlorinated paraffin, epoxidized oil, benzotriazole, calcium-zinc heat stabilizer, calcium carbonate, aluminum hydroxide, FR salts, NIR system pigments, isothiazolone derivative, silica.

Outer coating protective layer (6): polyurethane resin lacquer dispersed in water and at least one catalyst.

On a transfer paper, the compact intermediate layer was applied with cold pigments at a height of 0.19 mm, then pre-drying at a temperature of 180 °C for 15 s. Subsequently, on the compact intermediate layer with cold pigments, the lower foamed layer was applied at a height of 0.37 mm and pre-drying at a temperature of 180 °C for 15 s. Once both layers were applied and pre-dried, the tie layer was applied, calibrated at 0.5 mm. Finally, this bonding layer was joined with the textile component and it was taken to the oven at a temperature of 200 °C for 50 s and the transfer paper was removed in order to apply the protective outer coating layer. To do this, the outer layer of protective coating was applied to the PVC-coated textile with an application roller over the entire PVC-coated fabric and the PVC-coated fabric was dried at a temperature between 110 °C and l30 °C. C for 50s.

Example 7. Flexible PVC multilayer composite material with a nylon textile component (FIG. 1)

Lower textile component (1): 100% nylon

Tie Layer (2): PVC, DPHP, Adipic Acid Polyester, Calcium Carbonate, Aluminum Hydroxide, Antimony Trioxide, Silica, Isothiazolone Derivative.

Multi-layer top layer (3): Lower foamed layer (4): triaryl phosphate, barium-zinc base heat stabilizer, azodicarbonamide, aluminum hydroxide, zinc borate, antimony trioxide, isothiazolone derivative, white pigment.

Compact intermediate layer with cold pigments (5): PVC, DPHP, benzotriazole, tin carboxylate, calcium carbonate, aluminum hydroxide, zinc borate, FR salts, silica, NIR system pigments, isothiazolone derivative.

Protective layer of outer coating (6): first application of a layer of outer protective coating based on polyurethane dispersed in water and at least one crosslinking agent, and second application of a layer of outer protective coating based on polyurethane dispersed in solvent.

A compact intermediate layer with cold pigments was applied to a transfer paper at a height of 0.32 mm and pre-dried at a temperature of 180 °C for 20 s. Subsequently, the lower foamed layer was applied at a height of 0.67 mm and pre-dried at a temperature of 180 °C for 5 s. After the compact intermediate layer with cold pigments and the foamed lower layer had been applied, the bonding layer calibrated at 0.7 mm was applied. Finally, this layer of adhesive was joined with the textile component and it was taken to the oven at a temperature of 200 °C for 60 s to subsequently remove the transfer paper and continue with the application of the outer layer of protective coating.

As in the previous examples, this process is carried out in two applications. In the first, a protective layer of outer coating of polyurethane resin dispersed in solvent was applied by means of an applicator roller over the entire PVC-coated fabric, subsequently a pre-drying of the PVC-coated fabric was carried out at a temperature of 110°C for 40s. Subsequently, on the previous application, a polyurethane base and at least one catalyst dispersed in water were applied by means of application rollers on the entire PVC-coated fabric and the coated fabric was dried at a temperature between 120 °C and 140 °C for 60 s.

Example 8. Conditions and equipment to evaluate the radiation performance of multilayer composite materials To measure the thermal behavior of the multilayer composite materials of the present development, in particular of the materials of Examples 9 to 12, under a specific type of heat lamp (simulating sunlight), two methodologies were used:

- ASTM D4803-Prediction of Heat Accumulation in PVC Construction Products: This test method allows measurement of the temperature rise of a test sample compared to a reference sample under a specific type of heat lamp (i.e. , infrared reflective heat lamp). Allowing to predict the accumulation of heat (HBU) of the material against the exposure of solar radiation. The necessary experimental setup was reproduced according to ASTM D4803 to measure temperature rise.

Generally, the darker the product, the more energy is absorbed and the greater the heat buildup. However, even with the same apparent color, heat build-up can vary due to the structure of the material, the emission, absorbance, and reflectance of the material, the specific pigment system involved, and the way the pigment is formulated to color the surface. surface.

However, although this test method provides an estimate of the relative heat build-up between the test material and a reference material under certain defined severe conditions, it is important to note that it does not necessarily accurately predict the performance of materials under actual conditions. of use. The performance of any material depends on air temperature, the angle of incidence of the sun, clouds, wind speed, insulation, installation behind glass, exposure time, among other conditions.

Solar radiation simulation thermograms: In this test, samples were exposed under standard solar radiation conditions using a solar simulator (Newport Oriel® Sol 3A) using a 450 W xenon arc lamp on a bed of glass wool. .

The surface temperature rise of each sample exposed to these simulated solar conditions was measured every 2 min for 14 min and recorded with a Fluke Ti450® camera at an emissivity setting of 0.95. Once the time has elapsed heating under simulated solar radiation (14 minutes), the simulator was turned off and the cooling ramp of each sample was evaluated, measuring the surface temperature every 2 minutes for 14 minutes.

Example 9. Processability of cold pigments

To assess the importance of the processability of cold pigments on the radiation behavior of the multilayer material, pigment grinding was carried out using a ball mill system compared to grinding using a three-roll mill.

Ball mill system:

In the first case, the powdered pigment was mixed with an orthophthalate-type plasticizer and the mixture was left to stand for 7 h in order to wet the pigment particles with the plasticizer. After the wetting time, the mixture was stirred for 20 min in order to disperse the agglomerates generated during wetting and to better homogenize the dispersion. The above mixture was processed twice in a 3mm steel bead mill to ensure good pigment dispersion. The vehicleized cold pigment was subsequently incorporated into the compact intermediate layer of a multilayer material as described in Example 1, using a 2% PVC intermediate layer and identified with the reference #7870.

Three cylinder mill:

In the second case, the powdered pigment was also mixed with an orthophthalate-type plasticizer and the mixture was left to stand for 7 h to wet the particles, and after the wetting time, the mixture was stirred for 20 min to disperse the agglomerates. Subsequently, the mixture was processed once in a three-cylinder mill working at low pressure in order to avoid any alteration of the microstructure of the pigment. The cold pigment was incorporated into the compact interlayer of a multilayer material as in Example 1, using a 2% PVC interlayer and the sample was identified as #7871. The evaluation of the performance against infrared radiation of both materials was carried out in a solar simulator (Newport Oriel® Sol 3A) using a 450 W xenon arc lamp on a bed of glass wool as described in Example 8. The heating thermograms for the multilayer materials of references #7870 and #7871 are presented in FIG. 3. The results show the impact that the type of processing carried out on the cold pigments has on the performance of the material. In particular, reference #7870 in which the pigments were processed under more aggressive conditions, the material heats up just over 10 °C compared to reference #7871 in which the pigments were processed with a more regulated mechanical work analyzed Under the same conditions.

Example 10. Thermal behavior of the multilayer composite material

In order to evaluate the thermal performance of the multilayer composite material with cold pigments (NIR system) of the present development, a material like the one in Example 1 (#8744) was manufactured using a black NIR pigment. The manufactured material was compared with a conventional black multilayer material and with a reference material (commercial) also in black that declares to have a cold effect under the effect of simulated solar radiation (Newport Oriel® Sol 3A), as shown described in Example 8.

The thermograms of FIG. 4 show that the conventional material reaches a temperature up to 10 °C higher than the temperature reached by the material of the present development or the commercial reference material with cold effect after 14 min of exposure. On the other hand, the material of this development presents a slightly better performance than the commercial reference material with cold effect, which demonstrates the qualities of the developed material.

Example 11. Comparative test of heat accumulation

To evaluate the accumulation of heat and consequently the performance against the touch of the multilayer composite material, a sample like the one in Example 1 in black color (#26948) was manufactured and compared with a reference material (commercial) also in black color. and that it claims to have a chilling effect. Table 2 presents the measured and calculated heat accumulation results for the samples coded as #26948 and the reference material. FIG.5 shows the increase in temperature as a function of the time of exposure to the radiation of the lamp.

Table 2. Results obtained for the heat accumulation index according to ASTM D4803.

temperature of the temperature of the

Sample HBU (°C) Material (°C) Black Control (°C)

multilayer material

57.1 68.4 60 #26948 Material of

56.9 68.4 60 reference Thus, from Table 2 and FIG. 5, it can be seen that both samples have the same heat accumulation index result and followed the same temperature increase curve when exposed to lamp radiation, following ASTM D4803 (Example 8). On the other hand, by means of the solar radiation simulation test as described in Example 8, the maximum temperature reached during 14 min of simulated solar exposure and the cooling ramp once the simulator was turned off were determined (FIG. 6) for the multilayer material coded as #26948 and the reference material. As seen, from FIG. 6 it can be verified that both samples present similar heating and cooling behavior when subjected to a solar simulation test. In fact, both samples have the same maximum temperature when they were exposed for 14 minutes to the solar simulator equipment. Example 12. Thermal behavior of the multilayer composite material with an additional stamping layer

To evaluate the impact on the performance of the multilayer composite material of the present development, a material like the one in Example 3 was manufactured by placing a layer of printed in black with conventional pigments between the outer layer of protective coating and the compact layer with cold pigments (NIR system) in black. This material was compared to a material without the embossing layer and against a conventional material.

The thermal behavior of the three materials evaluated under the conditions described in Example 8 is shown in FIG. 7. The material with the stamping layer reaches a temperature of approximately 9 °C higher than the material without the stamping layer and in any case lower by at least 5 °C compared to the conventional material. In this sense, the substitution of conventional pigments for cold pigments could help improve the performance of the printing layer.

Claims

1. A multilayer composite material comprising: a lower textile component; a tie layer; a multilayer top layer; wherein the lower textile component and the upper multi-layer layer are bonded together by the tie layer; wherein the multilayer top layer comprises: a bottom layer; a compact middle layer with cold pigments and a protective outer coating layer.

2. The multilayer composite material according to Claim 1, wherein the multilayer top layer further comprises an embossing layer located between the cold-pigmented compact intermediate layer and the protective outer coating layer.

3. The multilayer composite material according to Claim 1, wherein the lower textile component is selected from cotton, polyester, nylon, cotton-polyester blend and other yarns from natural sources.

4. The multilayer composite material according to Claim 3, wherein the lower textile component is 100% polyester.

5. The multilayer composite material according to Claim 1, wherein the bonding layer comprises a polymeric base selected from polyurethane, acrylic or polyvinyl chloride and an additive.

6. The multilayer composite material according to Claim 1, wherein in the upper multilayer layer, the lower layer is foamed or non-foamed.

7. The multilayer composite material according to Claim 1, wherein the compact intermediate layer with cold pigments comprises a polyvinyl chloride polymeric base, plasticizers, cold pigments and an additive.

8. The multilayer composite material according to Claim 1, wherein the cold pigments are selected from anatase-type titanium dioxide (TiCh), di-iron trioxide (FeiCh)- cobalt blue spinel and aluminum (C0AI2O4), oxide iron and chromium (CnCri)- cobalt green spinel and titanium (C02T1O4), rutile type titanium dioxide (T1O2), antimony and manganese.

9. The multilayer composite material according to Claim 1, wherein the protective outer coating layer comprises a polymeric base of an acrylic or polyurethane polymer, a copolymer, a catalyst and optionally an additive.

10. The multilayer composite material according to Claim 2, wherein the print layer comprises at least one polymeric resin, a copolymer, a solvent and pigments.

11. The multilayer composite material according to Claim 2, wherein the print layer comprises an organic pigment carried in an acrylic resin and a solvent.

12. The multilayer composite material according to Claim 1 comprising: a lower textile component that is 100% polyester; a tie layer comprising polyvinyl chloride, dioctyl terephthalate, chlorinated paraffin, tin carboxylate, mineral fillers, and isothiazolone derivative; a lower foamed layer comprising polyvinyl chloride, dioctyl terephthalate and chlorinated paraffin, tin carboxylate, mineral fillers, isothiazole derivative, azodicarbonamide, and at least one pigment; a compact intermediate layer with cold pigments comprising polyvinyl chloride, dioctyl terephthalate, benzotriazole, tin carboxylate, mineral fillers, NIR cold pigments and isotriazole derivative; a protective outer coating layer comprising a polymeric base dispersed in aqueous or solvent base and at least one catalyst.