MXPA00000152A - Interlayer film for protective glazing laminates - Google Patents

Abstract

Optical and firescreening protective glazing laminates comprising fluoropolymer interlayer films are described. The films and their laminates comprise THV and blends of THV with FEP, ECTFE or ECCTFE, and modified with additives, such as coupling agents, pigment or color concentrates, and IR- or UV-light blockers, and may be subjected to a surface corona treatment. The films also may incorporate a fiber mesh for additional reinforcement.

Description

INTERMEDIATE LAYER FILM FOR TRANSPARENT LAMINATED MATERIALS PROTECTORS DESCRIPTIVE MEMORY The transparent protective material is used in many interior and exterior construction applications, including windows, glass partitions, doors, etc., for safety, impact resistance and fire resistance. The transparent protective material is usually a laminated structure consisting of an interlaminar structure of several glass sheets or polymer sections bonded together by means of an intermediate layer of a polymeric film placed between the sheets or the sections. One or more glass sheets can be replaced by optically transparent rigid polymer sheets, such as sheets of polycarbonate polymer. The intermediate layer of a relatively thick polymeric film is made which exhibits strength and ligability which will cause the glass to adhere to the intermediate layer in case of cracking or crashing. The transparent protective material that is made using common intermediate layer films (for example, polyvinyl butylate (PVB)), used in windows, doors and partitions must be sealed from the atmosphere to have any fire resistance that would prevent cracking or the breaking up of the glass in the event of a fire. In order to prevent the spread of fire, fire resistant materials including steel and other opaque materials and intumescent materials have been incorporated into the doors, windows and screens. However, these materials are heavy and do not provide the optical transparency necessary for applications of visually transparent material. The patent of E.U.A. A-5,244,709 discloses a technique in which an intumescent material, typically a hydrated alkali metal silicate film, is laminated between two vitreous glass sections of different thicknesses. This technique requires that both the film and the vitreous glass be quite thick (0.5-5.0 mm and 8.0-21.0 mm respectively) to give the necessary protection against fire and that once the localized heat limit for the film is reached, either by fire or by other means, the material becomes numb, rendering it unusable as well as optical laminate material. In many cases, additives are incorporated to reduce the temperature at which intumescence occurs. These additives can increase, in addition to reducing the intumescence temperature, both the turbidity and the cost of the final material. The patent of E.U.A. A-4, 978,405 discloses a method for manufacturing fire-protective transparent material, incorporating a wire mesh to a film of methacrylate resin and other additives, and laminating this combined film between glass sections. The addition of the wire mesh, while giving certain increased safety features, will affect and most likely decrease the optical quality of the final glass product. The addition of additives to the methacrylate resin, to increase the fire resistance, will also serve to decrease the luminous transmittance of the mechanical properties, create unacceptable amounts of turbidity and raise the cost of the final product. Furthermore, the incorporation of the wire mesh into the film creates an aesthetically undesirable effect and increases the weight and mass of the final glass section of fire protection, making the sections more difficult to handle. In the patent of E.U.A. A-4,681, 810, a sophisticated formulation is added to PVB that includes organic phosphate that forms charcoal and an organic phosphite that sequesters oxygen, to increase its fire resistance. The addition of a high additive load of the expensive PVB film increases the final cost of the material beyond the commercially acceptable point for many applications. It is described, in the patent of E.U.A. A-5,230,954, a laminate material of intermediate layer films of fluorocarbon resin in its specially formulated glass sections. Fluorocarbon resins (ethylene-propylene copolymer (FEP)) are bonded by thermocompression, especially fluorinated, tetrafluoroethylene hyperfluoroalkoxyethylene copolymer (PFA), polychlorotrifluoroethylene (PCFE), ethylene copolymer and tetrafluoroethylene (ETFE) and polyvinylene fluoride (PVDF)), to cover with glass at a pressure of 12 kg / cm2 at a temperature of 330 ° C. Due to the high temperatures and pressures required in this technique, specially formulated glass and a high temperature autoclave are required to alleviate the possibility of cracking and breaking glass during lamination. Each of these transparent protective laminates of the prior art (laminated material of intumescent material between vitreous glass, laminated wire mesh material between films loaded with methacrylate resin / adit and glass sheets, high loads of fire-resistant additives. in laminated materials of PVB film and laminated materials of fluorocarbon resins adhered to high temperatures and pressures on specially formulated glass) has significant disadvantages that are inherent in the construction and manufacture of the laminated material. It is an object of this invention to provide a fire-resistant fluoropolymer intermediate layer film for use in protective clear laminates produced at normal industrial lamination temperatures and techniques. This film has fire resistance and excellent optical qualities and high mechanical resistance. These films can be formulated to be transparent, semi-opaque or opaque, depending on their particular application. The films may incorporate a fiber reinforcing layer to increase the structural strength of the laminate. The invention is a protective transparent laminate comprising at least two layers of transparent protective material, at least one intermediate layer of fluoropolymer, the intermediate layer comprising at least 85% by weight of the tetrafluorothylene / hexafluoropropylene / fluoride copolymer of vinylidene (THV) and at least one reinforcement layer embedded in an intermediate fluoropolymer layer. The invention also includes a method for manufacturing transparent protective laminate materials, comprising the steps: a) exposing a fluoropolymer film comprising at least 85% by weight of THV copolymer or a corona discharge treatment at 0.045 and up to 0.76. watts / hour / square meter and in an inert gas atmosphere comprising at least one organic compound in the vapor phase; b) provide at least two layers of protective transparent material; and c) laminating an intermediate layer of fluoropolymer film to the sheets of clear protective material. The fluorocarbon film comprises at least 85% by weight of THV polymer: the thermoplastic elastomer polymer containing segments of tetrafluorothieniene (ECTFE), hexafluoropropylene (HFP) and vinylidene fluoride (VDF). THV polymers and various methods for making them are described in the U.S.A. No. A-3,235,537, A-3,132,123, A-3,635,926, A-3,528,954, A3,642,742 and A-4,029,868, the content of which is hereby incorporated by reference. THV polymers are block or graft copolymers consisting of an elastomeric soft segment (ie, hexafluoropropylene and vinylidene fluoride) and a hard fluoroplast segment (ie, tetrafluoroethylene). The preferred THV polymers are commercially obtainable polymers comprising a molar ratio of ECTFE: HPF: VDF of about 42-60: 20-18: 38-22. Also of use in the present are mixtures of THV with other fluoropolymers including, but not limited to, fluorinated ethylene-propylene copolymers (FEP), perfluoroalkoxy polymer (PFA), perchlorotetrafluoroethylene (PCFE), ethylene copolymer and tetrafluoroethylene ( ETFE), polyvinylidene fluoropolymer (PVDF), chloroethylene and tetrafluoroethylene (ECTFE), and dichloroethylene and tetrafluoroethylene (ECCTFE). Laminated materials composed of THV blends are used with other fluorinated polymers to offset the cost of the starting material and improve the strength properties of THV material. The added fluoropolymers exhibit greater mechanical strength and thermal stability which, when mixed with THV, gives a material having excellent fire resistance and thermal stability, in addition to improved mechanical strength. The mixtures (alloys) of THV and other fluoropolymers can be combined, and varying concentrations according to specific applications. For transparent protective laminates, at least 85% by weight of the film must be THV to maintain transparency. As used herein, "transparent" means a haze value of less than 4% by the method of ASTM D-1003, "semi-opaque" means a haze value of 4-25% and "opaque" means a value of Turbidity of more than 25%. As defined in the method of ASTM D-1003, "light or light transmittance" refers to the ratio of the light transmitted to the incident. "Turbidity" is the percentage of transmitted light that deviates more than 2.5 ° from the incident beam by forward propagation as it passes through the specimen. These values are recorded as light passing through a sample on a BYK Gardner turbidity meter. Transparent protective laminate materials are useful in the optical applications of laminated materials (eg windshield or glassware of military or emergency vehicles) in which visual clarity is important and laminated materials must be transparent; in light transmission applications (for example, certain architectural uses) in which semi-opaque features are acceptable. The untrained human eye is unable to detect a level of turbidity below 2-4%. For use in optical glass for fire protection or safety for most vehicles, windows and doors, acceptable turbidity values are below 4.0%, preferably below 3.0% and most preferably below 2.0% , measured according to the method of ASTM D-1003. Transparent opaque protective laminate materials may be useful in certain structures where the transmission of light of visual clarity is not desirable. Mixtures of 99-85% THV with 1-15% FEP show a turbidity value of < 4% and that's why they are transparent films. As the concentration of FEP in the mixture rises to 15-50%, the films become semi-opaque and show a turbidity value of 4-25%. The mixtures of THV with ECTFE or ECCTFE, when the secondary polymer is in the concentration of 1-30%, are also semiopaque. When 50-75% FEP concentrations are raised, the films lose their "cross vision" properties and become opaque. The opaque nature of the film provides a laminated glass material that has a haze value of >25%. Mixtures of ECTFE or ECCTFE, in concentrations of 30-70%, with THV also exhibit the opacity of the film, as previously described. Films containing mixtures of THV with > 75% FEP or 70% ECTFE or ECCTFE can not be bonded to glass satisfactorily and are therefore unsuitable for laminated glass materials produced in the conditions of industrial autoclaves. THV polymers possess many properties that make them outstanding candidates for intermediate layer fire protection films. THV exhibits exceptional resistance to flammability, excellent optical clarity, low adhesion temperature, chemical stability, glass bonding, moisture absorption, moisture sensitivity during storage and handling, high stability to ultraviolet light, and excellent flexibility and elongation. The excellent resistance to flammability of THV is due to the high percentage of fluorine atoms that surround the carbon-based structure and form an envelope that radically diminishes the fragmentation of the base structure and the combustion of the polymer. Preferred THV resins in the invention include molecular weights of the resin class ranging from 200,000 (THV-200G polymer, obtained from Dyneon, joint achievement of 3M Corporation and Hoechst Corp., Minneapolis, MN) to 500,000 (THV-polymer). 500G of Dyneon). The melt flow rates of these THV classes vary from 5 to 25 g / 10 min. @ 260 ° C and 5 kg of pressure, allowing the easy formation of films by extrusion. Also preferred are THV resin classes which have a polymer melting range of about 115-125 ° C and which comprise about 42 mol% ECTFE and which have a melting range of about 165-180 ° polymers. C and comprising approximately 60% mol of ECTFE. The choice of the most preferable class of THV depends on the particular needs for the desired applications. THV-200G possesses low molecular weight and low viscosity, and yet higher melt flow rate and elongation at the break point, the THV-500G has higher melting temperature and flexural modulus. In the present invention it is acceptable that the molten bath flow rate for the appropriate class of THV varies from 1.0 to 25.0, preferably from 3.0 to 20.0 and more preferably from 5.0 to 10. Due to the relatively high softening temperature ranges of THV polymers, the interlacing treatment typically required to extend the softening interval is not necessary. This allows for better film consistency and better optical quality. The ECTFE and ECCTFE polymers suitable for use herein are obtainable from Ausimont Corporation (Italy) under the Halar factory name. Other fluoropolymers used in the present invention can be obtained from Daikin (Japan) and Dupont (E: U.A.). The intermediate layer films preferably comprise an additive package containing coupling agents (from 0.1 to 2% by weight). The intermediate layer films may contain silane coupling agents (0.3-2.0% by weight) to improve adhesion of the intermediate layer film to the glass. An adhesive primer coating on the glass or plastic clear material can also be used. A preferred coupling agent for use with THV is vinyltriethoxysilane (VTES). Silane coupling agents do not improve the adhesion of the intermediate layer films to glass in concentrations below 0.3% by weight. The concentrations of silane coupling agent of more than 2.0% by weight increase the turbidity of the final material. The preferred range of the coupling agent is from 0.5% to about 1.7% by weight and the most preferred range of the coupling agent is from 0.7% to about 1.5% by weight of film. Other additives can be incorporated, such as pigments, coloring agents or concentrates, and infrared or ultraviolet light structures, to achieve special properties in transparent laminated materials and / or protective plastic. Unlike the PVB and methacrylate films that have been used in the previous laminated fire protection materials, the THV-based films, as described in the present invention, do not need plasticizers due to the characteristics of high resistance to fire. impact, nick and tear of the THV resin. In addition, the THV films described in this invention do not require additives to increase the fire resistance as seen in previous fire protection applications, due to the high resistance to flammability of the THV films. For the reinforcement layer, a fiberglass mesh can be incorporated between the layers of the THV film or based on THV to add structural support. A reinforcement is an improvement over the known metallic mesh for use in intermediate layer films, for example the U.S. No. A-4, 978,405. The metal mesh adds considerable weight to the final laminated glass product and decreases the aesthetic and optical properties of the laminated material. The addition of a fiberglass mesh does not appreciably increase the weight of the final product. Due to the white color and the relatively translucent appearance of the fiberglass mesh compared to the metal mesh, the fiberglass mesh retains more the optical qualities of the laminated material. The glass fiber mesh is preferably embedded between the layers of the film, which allows the THV or THV-based mixture to retain its high bonding to the glass. Additional structural support allows thinner films to be used for particular applications, reducing both waste and cost. The appropriate fiberglass mesh is obtainable from Bay Mili Limited, Bayex Division, Ontario, Canada, and Carl Freudenberg, Technical Nonwovens, Weinheim, Germany. Other reinforcing layers useful herein include, but are not limited to, fluoropolymer fiber mesh, Spectra fiber mesh (polyethylene terephthalate) and, in applications where appropriate, metal fiber mesh. The mesh may be in the form of woven, non-woven, knitted and hybrid mesh. Also useful are perforated sheets of reinforcing materials sized to allow the needle to be embedded within the intermediate layer film during assembly of laminate. The reinforcing layer is preferably 0.025 to 0.51 mm thick. The transparency and turbidity in the light of the intermediate layer film and the glass laminate depend, in part, on the thickness of the intermediate layer film. The minimum thickness of the intermediate layer will be a function of the security requirements for the selected application. For the transparent protective laminate materials used in vehicle glass and architectural glass, the intermediate layer films of the fluoropolymer preferably have a thickness of 0.125 to 1.0 mm. The preferred thickness is determined by impact and penetration resistance tests and the ability of the laminate to retain the glass debris upon breaking. An intermediate layer film of high impact resistance and a reinforcing layer allow a reduction in the thickness of the films necessary to satisfy a specified safety requirement. As an added benefit of the invention, the reduced film thicknesses possible when intermediate fluoropolymer layers are used also weaken the haze value for the protective clear laminate. In order to manufacture the intermediate layer films of the invention, the polymers can be mixed with the coupling agent and other additives in a high speed dry mixer and combined using a molten bath combiner extruder. The joint rotator and doubleworm extruder model ZSK-30 was used in the present invention, with 30 mm worms made by Werner Pfleiderer Corporation, but any other suitable combustion extruder can be used. The combining machine should provide uniform mixing of the basic aminoplast resins, with relatively small amounts of the required additives. In a preferred method for producing the films useful in the invention, a molten bath exiting the extruder is formed as strips using a die plate with a number of holes, eg, 4-6 holes for a relatively small die plate, which may be provided with a screen filter to remove any gels or molten bath impurities. The strips can be cooled in a water bath; Cut into pellets of typical size (1-4 mm in diameter and 2.5-5 mm in length) and dry it. The formulations can be stored in the form of pellets and extruded as a film as needed. In a suitable process, the extrusion lines of the films are equipped with flat extrusion dies and rolls or drums used to calibrate the thickness and to cool the continuous film roll. After cooling, the film is rolled into rolls. The thickness and width of the intermediate layer film will depend on the particular application, the thickness typically varying in the range of about 125 μm to 1000 μm. The intermediate layer film according to the present invention can be laminated to mineral or polymeric glass substrates using the same technologies and conditions as those used for conventional PVB films of intermediate layer of transparent protective and security material. The laminates of good quality mineral glass can be manufactured in a vacuum autoclave at a temperature in the range of 100 to 300 ° C, preferably 140 ° C to 170 ° C and pressures in the range of 12 bar to 23 bar. Preferred autoclave lamination conditions include temperatures in the range of 150 ° C to 165 ° C and pressures in the range of 13 bar to 17 bar. In a typical procedure in which mineral glass is used, the intermediate layer film is placed between the glass plates and cut to the appropriate size. The interlaminar glass / film / glass structure is sealed in a vacuum bag and a vacuum is applied to the bag until all the air is removed. The vacuum bag containing the interlaminar structure is placed in an autoclave and treated as described above. The glass or polymeric substrates useful for lamination to the films of the invention include all transparent materials known in the art of transparent protective or security material. Preferred lamination substrates include fire or impact resistant substrates, including, but not limited to, borosilicate glasses, soda-lime glasses, tempered mineral glasses, polycarbonate, polyacrylate and combinations thereof. Surface treatments of the lamination substrates that are known in the art can be added for their abrasion resistance, thermal reflectance and the like. Lamination substrates can be reinforced with wire mesh or other reinforcement materials. To improve the adhesion of the films to the mineral glass, a solution (eg, 0.5-10% by weight) of a siloxane primer (eg, aminotripropylsiloxane) in water and a water / alcohol mixture (eg. example, sopropanol), for coating the contact surfaces before autoclaving. The application can be by immersion, spraying or brushing, followed by drying immediately afterwards wait for 2-5 minutes at 120-180 ° C. For optimum adhesion, a monomolecular layer of silane is applied and the amount per surface area varies according to the chemistry and surface area of the substrate and the intermediate layer and the wetting characteristics of the silane used. The formula can be used g substrate X specific surface area of the substrate in m2 / g g silane = silane specific wetting area in m2 / g to calculate the optimum amount of silane coating that is needed to adhere the intermediate layer to the substrate.

EXAMPLES The following examples are a specific illustration of the embodiments of the invention. These examples illustrate the invention and are not intended to limit the scope of the invention.

Conformation to films of THV formulations and THV / Fluoropolymer mixtures Procedure # 1 THV-based formulations and THV / FEP polymers were produced, by mixing their melted baths with a coupling agent using a ZSK-30 double worm extruder made by "Wemer Pfleiderer Co.", of Ramsey, USA, equipped with two joint rotating worms with a diameter of 30 mm. The formulations were premixed in a high speed (turbo) mixer at 300 rpm for 20 minutes and then fed to the twinworm extruder. The ZSK-30 extruder is equipped with a sieve filter followed by a sieve plate having four holes. All formulations were extruded in strips. The strips were cooled in a water bath and pellets 2.5-3 mm in diameter and 3-4 mm in length were then cut. For THV formulations, the double worm extruder had the following temperatures in the drum: feeding zone # 1 - 100-115 ° C, drum zone # 2 - 145-155 ° C, barrel zone # 3 - 170- 180 ° C, drum area # 4 - 190-200 ° C, drum area # 5 - 200-210 ° C, die plate - 205-225 ° C. The speed of the worms was 96 rpm. The pellets were dried at 75-80 ° C.

Procedure # 2 For THV / FEP blend formulations, the double worm extruder had the following temperatures in the drum: feed zone # 1 - 210-225 ° C, drum zone # 2 - 255-270 ° C, zone drum # 3 - 285-300 ° C, drum area # 4 - 290-305 ° C, drum area # 5 - 300-315 ° C, die plate - 300-315 ° C. The speed of the worms was 70 rpm. The pellets were dried using a stream of air at room temperature.

Procedure # 3 For mixture formulations of THV / ECTFE and THV / ECCTFE, the double worm extruder had the following temperatures in the drum: feeding zone # 1 - 170-185 ° C, drum zone # 2 - 205-215 ° C, drum area # 3 - 225-240 ° C, drum area # 4 - 230-245 ° C, drum area # 5 - 235-250 ° C, die plate - 245-260 ° C. The speed of the worms was 75 rpm. The pellets were dried using a stream of air at room temperature. In the extruder # 1 process, the films were formed into the pellets extracted using the lines of a film that consisted of a single worm extruder made by Extrusion Systems Limited (ESL), United Kingdom. The worm of the ESL extruder had a diameter of 32 mm and a length with respect to the worm of 24 diameters. The extruder was equipped with a flat extruder die having a hole which was approximately 32 cm wide. Films with two thicknesses, 0.13 mm and 0.18 mm, were produced with the formulations. The drum of the single worm film extruder was divided into four heating zones, progressively increasing the temperature of polymeric material to the adapter, the filter and the flat die. For THV-200G pure films, the drum temperature was maintained in each of zones 1-4 in the ranges of 100-110 ° C, 140-155 ° C, 165-180 ° C and 180-190 ° C respectively. The adapter temperature was maintained at approximately 190-200 ° C. The die temperature was maintained at approximately 190-200 ° C in the intermediate sections, at 190-200 ° C on both edges of the die and at 195-205 ° C on die lips. For THV-500G, the temperature of the drum was maintained in each of zones 1-4 in the range of 185-195 ° C, 235-240 ° C, 255-265 ° C, 260-270 ° C, respectively. The adapter temperature was maintained at approximately 250-260 ° C. The die temperature was maintained at approximately 230-240 ° C in the intermediate sections at 240-250 ° C on both edges of the die and at 245-255 ° C on die lips. The THV / FEP mixtures required a much higher extrusion temperature. Drum temperatures were maintained for THV / FEP mixtures in each of zones 1-4 in the ranges of 215-225 ° C, 250-265 ° C, 270-280 ° C, 285-295 ° C, respectively. The temperature of the adapter was maintained at approximately 285-290 ° C. The die temperature was maintained at approximately 290-295 ° C in the intermediate part of the die and 295-300 ° C at the edges of the die lips. THV / ECTFE and THV / ECCTFE mixtures required slightly lower temperatures than THV / FEP, but at higher temperatures of pure THV. The drum temperatures were maintained for the THV / ECTFE and THV / ECCTFE mixtures in each of zones 1-4 in the ranges of 205-215 ° C, 225-235 ° C, 230-240 ° C, 230- 240 ° C, respectively. The adapter temperature was maintained at approximately 225-230 ° C. The die temperature was maintained at approximately 230-235 ° C in the middle part of the die and 235-240 ° C at the edges of die lips.

The temperatures in each zone were varied in a relatively narrow range according to the molten bath flow rate of the resin used. The worm speed was maintained between 23.0 rpm for 0.13 mm thick films and 23.3 rpm for 0.18 mm thick films. Each film was extruded and cooled using a 3 roll roller head and wound on 7.6 cm bores. In the extruder # 2 process, the extracted pellets were formed as films using a cast-film line based on a single worm extruder made by Davis-Standard. The worm of the Davis-Standard extruder had a diameter of 51 mm and a length with respect to the worm of 24 diameters. The extruder was equipped with a flat extruder die having a hole which was approximately 140 cm wide. THV-200G films were made in three thicknesses, 0.18 mm, 0.25 mm and 0.36 mm. The drum of the single worm film extruder was divided into four heating zones, progressively increasing the temperature of the polymeric material to the adapter, the filter and the flat die. The temperature of the adapter was maintained in each of zones 1-4 in the range of 110-125 ° C, 155-170 ° C, 180-200 ° C, and 190-210 ° C, respectively. The temperature of the adapter was maintained at about 195-205 ° C. The die temperature was maintained at approximately 190-200 ° C in the intermediate sections, at 195-205 ° C on both edges of the die and at 195-200 ° C on the sides of the die.

The temperatures in each zone were varied in a relatively narrow range according to the adversity of the molten bath flow of the resin used. The worm speed was maintained at approximately 25.0 rpm for all films. Each film was extruded and cooled using a head with 3-roll casting rolls and wound on 7.6 cm bores.

Lamination of fire protection film between glass Laminated mineral glass samples were prepared using glass sheets of soda-lime-silicate 3 mm thick and dimensions of 7.5 x 7.5 cm that were cleaned using isopropyl alcohol to remove dust, grease and other contaminants on the glass surface. For lamination, a piece of film was cut to obtain a sample that was 7.5 x 7.5 cm. This film sample was placed between two clean glass plates and the entire interlaminar glass structure was then placed in a laboratory press, model 3891, manufactured by Carver, Inc., Wabash, Indiana, equipped with a temperature control system. -pressure-time monitored by a microprocessor. A heat and pressure program was used to simulate autoclave conditions typical of optical lamination manufacturing. The heating melted the surfaces of the film during the lamination process, helping to adhere the polymeric film to the glass substrate. For some tests, a set of full-sized glass laminate material (100 cm x 100 cm) was produced using an industrial autoclave set at 140 ° C and 12 bar vacuum pressure.

Test Procedures for Glass Laminates Samples of laminated materials were tested according to the above description and in terms of transmittance properties of light, turbidity, impact and fire protection. The turbidity values of the laminated materials were measured, using a Haze Gard® Plus turbidity meter, obtained from BYR Gardener Corporation (E.U.A., Germany), as indicated in the method of ASTM D-1003. The light transmittance was measured using the ANSI Z26.1 T2 standard and the turbidity was measured for examples 1 and 2, using the ANSI Z26.1 T18 standard. The impact properties of the laminated materials were measured using the following typical tests: impactor test -CEN / TC129 / WG13 / N42; and ball drop tests -DIN 52338; sphere drop -ECE R43 A6 / 4.2 and sphere drop - NF P 78406. Fire resistance was measured using the ISO 834 standard test. According to this standard, the fire protection glass must pass 30 minutes of tests against fire.

EXAMPLE 1 Films of different thicknesses of resin THV-200G, obtained from 3M Corporation and containing 0.7-1.5% by weight of coupling agent VTES, obtained from OSI Specialty Chemicals, West Virginia, were processed using procedure # 2 and tested for identify the optimal thickness in terms of safety and performance. Acceptable results of the safety test with falling sphere and the fire resistance test were obtained, in a film thickness of at least 0.25 mm. This compares favorably with commercial PVB interlayer films for certain laminated safety glass materials that are usually at least 0.76 mm thick. Table 1 shows the turbidity values for THV films. The turbidity of the THV film was < 4%, certainly within the requirements for transparent optical laminate materials.

TABLE 1 Laminated materials of films made with THV-200G resins (a) - Three (3) reps of the ball drop test were conducted. Approval was given if the heavy object did not penetrate the glass plates in the laminated material (penetration of a glass plate was acceptable). The test of the drop of wait involves dropping the weight of the sphere from a certain height on a laminated material that is placed on a pedestal. The following weights / heights were used: 1-03 kg / 6.0 meters 2.26 kg / 4.0 meters 4.10 kg / 1.5 meters (b) - Provided approval in the fire protection test, if the laminated material carried > 30 minutes of a fire situation.

EXAMPLE 2 Films of different thicknesses of THV-500G resin, obtained from 3M Corporation and containing 0.7-1.5% by weight VTES coupling agent, obtained from OSI Specialty Chemicals, West Virginia, were extruded using procedure # 1 to identify the optimum thickness and in terms of safety and cost. The results of the test are impact of the sphere drop and the results of the fire resistance test for the THV film are acceptable at an intermediate layer film thickness of less than 0.25 mm. THV-500G films possessed better mechanical properties but identical fire resistance properties than films THV-200G. The values of turbidity of the films was 4%. The light transmission of the THV-200G sample (0.18 mm film) was 86.4%; and of the THV-500G sample (0.18 mm film) was 87.2%. tests of resistance to the commission and of fall of sphere realized on samples of THV-200G (bag of 50 kg released from 1.2 meters) on a film of 0.18 mm and a film of 0.24 mm demonstrating an acceptable resistance of the films to both thicknesses . A marble of 26 kg released from varying heights on a 0.18 mm film went through breaking at 3 meters and at 4 meters for a 0.24 mm film.

EXAMPLE 3 Films were composed of THV-200G and FEP (FEP class NP-20 obtained from Daikin Corporation, Japan) using procedure # 2 and examined to determine the optimum concentration of FEP to give increased mechanical strength, but to minimize the turbidity of the film. When the concentration of FEP in the mixture was increased above 15%, the optical light transmittance decreased from low of 75% and the turbidity of the mixed film rose above 4%. The blends made the FEP concentration to be 1-15% of the local mix produced films with a haze value of less than or equal to 4%, allowing it to be used as transparent optical laminates. The results of the tests are shown in table 2.

EXAMPLE 4 THV / FEP mixtures containing 15-50% FEP (NP-20 from Daikin Corporation, Japan) and extrudates using procedure # 2 produced films that were semi-opaque. These films exhibited for 4-25% turbidity light. Although the inadequate turbidity of these films for transparent laminate materials, the mechanical and fire resistance properties of the intermediate layer film were acceptable. The results are shown in table 2.

EXAMPLE 5 THV / FEP mixtures containing 52 to 75% FEP (NP-20 from Daikin Coporation, Japan) and extruded using procedure # 2 produced films that did not exhibit optical transparency and were opaque. The intermediate layer films exhibited turbidity values > 25% Although the turbidity made these films for optical laminates inadequate, the fire resistance and mechanical properties of the intermediate layer films were acceptable. The results of the tests are shown in Table 2. In the absence of a coupling agent, the mixtures of the TH1, the THV mixtures in which the concentration of FEP was > 75% did not bind adequately to substrates and typical conditions of autoclaving.

TABLE 2 CONCENTRATIONS OF MIXTURES AND TURBIDITY VALUES THV / FEP MIXTURES The turbidity was measured using the method of ASTM D-1303.

EXAMPLE 6 THV / ECTFE mixtures containing 1-30% ECTFE (Halar 300 resin obtained from Ausimont Corporation, Italy) and extruded using process # 3 produced films that were semi-opaque. The films were displayed with turbidity values of 4-25%. Although these films were unsuitable for transparent laminate materials due to turbidity, the fire resistance and mechanical properties of the films were acceptable. The results of the samples are shown in Table 3.

EXAMPLE 7 THV / ECTFE mixtures containing 30-70% ECTFE (Halar 300 resin obtained from Ausimont Corporation, Italy) and extruded using procedure # 3 produced films that were semi-opaque. The films were displayed turbidity values of > 25% Although these films were unsuitable for transparent laminate materials due to turbidity, the fire resistance and mechanical properties of the films were acceptable. The results of the samples are shown in Table 3.

EXAMPLE 8 The THV / ECCTFE mixtures containing 1-30% ECCTFE (Halar 353 resin obtained from Ausimont Corporation, Italy) and extruded using the # 3 procedure produced films that were semi-opaque. The films were displayed with turbidity values of 4-25%. Although these films were unsuitable for transparent laminate materials due to turbidity, the fire resistance and mechanical properties of the films were acceptable. The results of the samples are shown in Table 3.

EXAMPLE 9 THV / ECCTFE mixtures containing 30-70% ECCTFE (Halar 300 resin obtained from Ausimont Corporation, Italy) and extruded using process # 3 produced films that were semi-opaque. The films were displayed turbidity values of > 25% Although these films were unsuitable for transparent laminate materials due to turbidity, the fire resistance and mechanical properties of the films were acceptable. The results of the samples are shown in Table 3.

TABLE 3 THV / ECTFE MIXTURES AND THV / ECCTFE EXAMPLE 10 Coupling agents were used to increase the ligability of the THV and THV / FEP films to a sheet without pretreatment of the surface of the sheet with primers. Several formations were prepared using THV -200G (3M Corporation) with coupling agents, and vinyl triethoxysilane (VTES) or aminopropyl triethoxysilane (APTES), both obtained from OSI Specialty Chemicals Virginia of the Northeast. Films were prepared by procedure # 1 and the components of the films were mechanically stirred for 1 hour before extortion to ensure uniform mixing. One of the films was treated with the corona discharge treatment described below of example 13. The evaluation of those films used an APTES incorporation to the fluorinated resin producing films that were yellow in color and hue. The addition of VTES to the films produced films that were colorless. The results of the turbidity test are shown in Table 4 for samples of THV-200G not combined.

TABLE 4 The corona treated sample was prepared as described above and treated as described in example 13. The light transmission of the nominated product containing the corona treated sample was 89.65%.

EXAMPLE 11 To increase the structural stability without increasing the thickness of the film, glass laminates containing THV-200G and the strength of glass fiber and polyester fiber were produced. Samples of glass fiber and polyester fibers of different mesh and strand sizes were obtained from Bay Mills Limited, Bayex Division (Ontario, Canada). Non-woven glass fiber samples were obtained from Cari Freudenberg, Technical Nowovens (Weinheim, Germany). A fiberglass fabric was placed in matte mesh material between two 0.125 mm layers of THV-200G film, allowing a finished film thickness of approximately 0.25 mm. This interlaminar film / fiber / film structure was heated to 200 ° C and compressed between sheets of tetrafluoroethylene in a Carver Laboratory press at approximately 70.31 kg / cm2 for 30 minutes to form a single unit, which is then valid between two plates of glass as described above. The luminous section of the laminated products was measured as described above and the results are shown below in table 5. The reinforcement within the final laminate allowed better structured support and thinner film requirements (to meet the requirements of the test against impacts) without significant loss of light transmission.

TABLE 5 EXAMPLE 12 To increase the structural stability without increasing the thickness of the film, glass laminates containing THV-200G, 0.7-1.5% by weight VTES accumulation agents and metal meshes were produced. Aluminum protection mesh was obtained from BayMills Limited. Other metal meshes, including several brass, copper and bronze, in a variety of wire and mesh sizes, were obtained from Delker Corporation (USA). The metal mesh was placed between two 0.125 mm layers of THV-200G transmitting a final film thickness of approximately 0.25 mm. This superposed film / fiber / film product was heated and compressed to form a simple unit as described in Example 12, which was then laminated between two glass plates using the lamination conditions previously described. As with the fiberglass reinforcement, the metal mesh within the final laminate allowed low structural support and a thinner film was adequate to meet the requirements of the intermediate layer for impact testing.

EXAMPLE 13 Resin films of THV-200G obtained from 3M Corporation were extracted, using procedure # 2 to a thickness of 0.38 mm and exposed to corona discharge in an acetone / nitrogen atmosphere to increase the addition of the fluoro polymer film to the sulphate of glass. The corona discharge treatment method as set forth in the US patent was used. No. -A-3,676,181 (Kowalewski), to treat the film. The atmosphere of the wrapped treatment equipment was 20%, by volume, of acetone in nitrogen and the gas flow was continuous. The THV-200G film was continuously fed to the envelope and subjected to 0.045 and up to 0.76 watts / hours / square meter of the film surface. The visual clarity of the film did not change as a result of corona treatment. At the end of the corona treatment, in the fluoropolymer film laminated on soda-lime glass it exhibited a blistering phenomenon in which the film did not adhere completely to the glass sulfate of many areas. Piston tests of the un-treated corona discharge material (conducted as described in U.S. Patent No.A-4, 952,460 to Beckman, et al) showed piston recordings of 0, where no glass remained about the movie after the impact. The corona discharge treatment warned the mission of the film to glass to produce a laminate material exhibiting an acceptable lamination model and piston test ratings of 1-2, in which 5-10% of the glass remained attached in the movie after the impact.

EXAMPLE 14 The THV-500G resin film obtained from 3M was obtained Corporatio, to a thickness of 0.38 mm using procedure # 2 and exposed to corona discharge in an acetone / nitrogen atmosphere as described in example 13 before lamination of the fluoropolymer film to a glass substrate.

In the laminations of the THV-500G film at the end of soda-lime, the laminate exhibited a complete delamination of the film to the glass substrate. As the samples not treated by corona discharge of THV-200G, the laminated materials exhibited a piston rating of 0. It was found that the exposure of the THV-500G film to corona discharge increased the adhesion of the film to the glass. produce a laminated material with a diminished support effect. The adhesion of the THV-500G film treated by corona discharge showed an adhesion piston rating of 0-1, leaving 0-5% glass after impact.

EXAMPLE 15 THV-200G and THV-500G formulations were extruded to a silane coupling agent (VTES) in concentrations of 0.7-1.5% by weight, using procedure # 2 and exposed to corona discharge as previously described in the example 13. In the absence of corona treatment, the laminated materials exhibited inadequate adhesion for the tests, showing supported and severe delamination. Laminated materials containing THV-200G? / TES film that were treated with corona discharge exhibited little or no support or visual delamination, even for prolonged periods. These THV-200G / VTES laminates treated with corona discharge exhibited a piston value of 4-5, where up to 50% of the glass from which the laminated materials are used after impact. Laminated materials containing THV-500G / VTES treated with corona discharge exhibited a piston rating of 1-3, where 5-15% of the glass remained on the surface of the laminate. An increase of the silane content in THV-200G to 1.0% increased the piston values up to a rating of 4-5.

Claims (20)

NOVELTY OF THE INVENTION CLAIMS

1. - A protective transparent laminate comprising at least two layers of transparent protective material, at least one intermediate layer of fluoropolymer comprising at least 85% by weight of tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, and at least one reinforcement layer embedded in the intermediate layer of the fluoropolymer.

2. Transparent protective laminate product according to claim 1, further characterized in that the layers of transparent protective material of the group consisting of polycarbonates, soda glass, crystallized glass, borosilicate glass, ceramic glass, acrylic and combinations thereof are selected. the same.

3. Transparent protective laminate product according to claim 1, further characterized in that the fluoropolymer layer also comprises at least one fluoropolymer selected from the group consisting of FEP; PFA, PCTFE, ETFE, PVDF, ECTFE and ECCTFE, and combinations thereof.

4. Transparent protective laminate product according to claim 1, further characterized in that the reinforcing layer of the group consisting of glass fiber mesh, Spectra fiber mesh, fluoropolymer fiber mesh, thermoplastic mesh comprising fire retardant and metallic fiber mesh, and combinations thereof.

5. Transparent protective laminate product according to claim 4, further characterized in that the reinforcing layer of the group consisting of woven, nonwoven, knitted and hybrid meshes is selected.

6. Transparent protective laminate product in accordance with claim 1, further characterized in that the reinforcing layer is transparent.

7. Transparent protective laminate product according to claim 1, further characterized in that the laminated material has a maximum of 4% turbidity.

8. Transparent protective laminate product according to claim 1, further characterized in that the fluoropolymer layer is a two-layer laminated material of fluoropolymer film having a middle layer consisting of the reinforcing mesh.

9. Transparent protective laminate product according to claim 8, further characterized in that the fluoropolymer layer is less than 0.51 mm thick.

10. Transparent protective laminate product according to claim 1, further characterized in that the transparent protective material is glass.

11. - Transparent protective laminate product according to claim 1, further characterized in that the laminated material is a fireproofing that has sufficient thermal resistance to meet the fire protection standards of ISO 834. 12.- Transparent protective laminate product according to claim 11, further characterized in that the fire shield comprises at least two layers of protective transparent material, each approximately 1 to 10 mm thick, and an intermediate fluoropolymer layer of 85-100% by weight of THV and 0 to 15% by weight of a polymer selected from the group consisting of FEP, PFA, PCTFE, ETFE, PVDF, ECTFE and ECCTFE, and combination thereof, and a glass fiber reinforcing mesh, having the intermediate layer of fluoropolymer a thickness of approximately 5 to 25 mm. 13. Transparent protective laminate product according to claim 1, further characterized in that the laminated product is a transparent material resistant to impacts that has sufficient impact resistance to meet the standards of protection of Din 52338. 14.- Laminated product transparent protector according to claim 13, further characterized in that the transparent impact resistant material comprises at least two layers of protective transparent material, each about 2 to 10 mm thick, and an intermediate fluoropolymer layer of 85-100% by weight of THV and 0 to 15% by weight of a polymer selected from the group consisting of FEP, PFA, PCTFE , ETFE, PVDF, ECTFE and ECCTFE, and combination thereof, and a fiberglass reinforcing mesh, the fluoropolymer intermediate layer having a thickness of about 5 to 25 mm. 15. Transparent protective laminate product according to claim 1, further characterized in that the fluoropolymer layer also comprises at least one additive selected from the group consisting of coupling agents, pigments, IR blocker, UV blocker and combinations of the same. 16. Transparent protective laminate product according to claim 15, further characterized in that the fluoropolymer layer comprises at least one silane coupling agent. 17. Transparent protective laminate product according to claim 16, further characterized in that the fluoropolymer layer comprises vinyltriethoxysilane. 18. A method for manufacturing protective transparent laminate materials, comprising the steps: a) exposing a fluoropolymer film comprising at least 85% by weight of THV copolymer to a corona discharge treatment at 0.045 and up to 0.76. watts / hour / square meter in an inert gas atmosphere comprising at least one organic compound in the vapor phase; b) provide at least two sheets of transparent protective material; and c) laminating an intermediate layer of the fluoropolymer film to the sheets of transparent protective material. 19. The method according to claim 18, further comprising the step of adding a silane coupling agent to the fluoropolymer film layer prior to lamination. 20. The method according to claim 18, further characterized in that the intermediate layer of fluoropolymer film is laminated to the sheets of transparent protective material in a vacuum autoclave at 100 and up to 200 ° C for 20 to 60 minutes.