WO2019194755A1

WO2019194755A1 - Extrudable compound for aluminium composite panel at a2 class fire resistivity and method of making aluminium composite panel with thereof

Info

Publication number: WO2019194755A1
Application number: PCT/TR2018/050146
Authority: WO
Inventors: Hüseyin Öztürk
Original assignee: Hdo Plastik Sanayi Ve Ticaret Limited Sirketi
Priority date: 2018-04-05
Filing date: 2018-04-05
Publication date: 2019-10-10

Abstract

The present invention relates with the production formulation and method of thermoplastic resin compounds for manufacturing of aluminum-plastic composite panel at A2 class fire resistivity according to Standard of EN 13501-1. The said thermoplastic resin compounds can produced via a continuous single or twin-screw compounder, banbury and co-kneader in pellet, granule form. The said compounds can be reprocessed into desired shape by a twin-screw extruder or single-screw extruder coupled with flat die at conventional aluminum composite panel manufacturing line. The compounds said in this invention provide cost effectiveness, flexibility to aluminum composite panel manufacturers. Thus, the compounds unveiled in this invention allow manufacturing aluminum composite panel with no need of core materials in coil form requiring machine investment.

Description

EXTRUDABLE COMPOUND FOR ALUMINIUM COMPOSITE PANEL AT A2 CLASS FIRE RESISTIVITY AND METHOD OF MAKING ALUMINIUM COMPOSITE PANEL

WITH THEREOF

Field of the Invention

The present invention relates to extrudable thermoplastic resin compound for building panel at A2 class fire resistivity. The building panel such as a flooring panel or wall panel and the use thereof to form floors, walls, cladding, etc., by assembling a plurality of the panels and thermoplastic core materials produced by the extrudable thermoplastic resin compound at A2 class fire resistivity according to EN 13501 -1 .

Description of the Related Art

In recent years, several major fires occurred in high-rise buildings involving rapid fire spread and smoke and toxicity upon the exterior walls and facades, and caused severe damage and loss. The extensive use of combustible insulation materials without proper fire protections and barriers were believed to contribute to the uncontrollable fire spread in the high-rise buildings.

If a fire is able to find sufficient flammable materials, it will quickly spread through an area. It is therefore crucial to use materials of limited combustibility on key surfaces within a room, such as ceilings and walls. The use of such materials can dramatically reduce the speed flames spread through an area as well as minimize their contribution to the fire.

The European standard EN 13501-1 : Fire classification of construction products and building elements-Part 1 : Classification using test data from reaction to fire tests provides a number of performance criteria to measure the fire characteristics of building products. These cover spread of flame and contribution to fire as well the generation of smoke and the production of burning droplets esc. as seen detailed in Table-1

According to EN 13501 -1 , total heat release rate of A2 class fire resistive aluminium composite panel (ACP) material should be equal or less than 3 MJ/kg. With this point of view, it is obvious that manufacturing facilities of composite panels having fire resistivity at A2 class or better will become more important. Regarding with manufacturing of A2 class composite panels, the authors of patent CN201399940 clearly expressed that core material of A2 class composite panels contains inorganic materials in large number and high percentage, resulting in the situation that core materials of A2 class ACP may not be processed with a common manufacturing equipment such as banbury, single screw, co-rotating or counter rotating twin screw extrusion line. Main reason behind the unprocessability of A2 class ACP core material is high filling ratio of polymeric materials given rise to deterioration of structure integrity of the compounds. Single screw extrusion line coupled with a flat die is the most common method is used by manufacturer of B1 or B2 class ACP.

Because of unextrudable structure of A2 class compounds, different engineering approaches have taken place at ACP manufacturing. One of the most popular solution is using A2 class core material in coil form having cloths to be able to obtain structure integrity. It is clear that using core materials in coil form have resulted in requirements of investing for a new machine or modifying existing production line. Investment cost, loss at productivity and less flexibility of production, difficulties of adhering coil onto aluminum sheets, storage cost of A2 coil and availability of A2 coil at required time are the disadvantages of the manufacturing technique of ACP at A2 class with using coil.

Instead of using A2 class fire resistive coil core, extrudable A2 class fire resistive compounds in granule or pellet form has crucial importance for ACP manufacturer. Extrudable A2 compounds can be used directly in extrusion line coupled with flat die that already used for B1 and/or B2 class fire resistive ACP manufacturing. On the other hand, using A2 extrudable compound in manufacturing line allows increasing productivity, production speed, and flexibility. Besides that manufacturers of ACP can directly be use existing facilities without any additional investment nor modification in case of using A2 extrudable compounds. Coil usage at ACP manufacturing cause batch-wise manufacturing, while A2 extrudable compounds results in continuous manufacturing methods which ensures uniform product quality with low cost.

The patent numbered CN201399940 disclose a utility to be able to produce A2 class fire resistive ACP in a continuous manner. However, the compounds used for core material coupled with fabric to ensure structure integrity, in addition, reprocess ability or extrudablity was not a major concern of this patent.

Another patent CN205255632 suggested obtaining a core material with A2 class fire resistivity using 10%acrylic acid and 90% inorganic materials. The method to prepare core material is not mentioned in the patent. Again, process ability and extrudability is not the main subject of the patent.

Patent CN102242559 relates to color mirror fireproof aluminum-plastic composite panel at A2 fire resistivity. However, manufacturing of A2 class fire resistive core material is out of scope of the subject of the patent.

Another patent CN102585337 claimed manufacturing of extrudable core material at A2 class fire resistive for panels according to standard GB20286-2006. The authors of the patent clearly express that core material mentioned in the patent can only meet the requirements of total heat release rate equal or less than 4 MJ/kg, not than 3 MJ/kg. Therefore, it is obvious that core material mentioned in the patent cannot be classified as A2 class fire resistive material according to European standard EN 13501 -1 that require total heat release rate must be 3 MJ/kg. To our best knowledge, extrudable A2 class fire resistive thermoplastic core material compounds in comply with the European standard EN 13501 -1 , are not available and could not be produced by a company. For the first time, this patent disclose the extrudable thermoplastic compounds used for ACP manufacturing at A2 class fire resistivity according to EN 13501 -1.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT

Fire-resistive rating can be described as the time that the material or construction will withstand fire exposure as determined by a fire test made in conformity with the standard methods of fire tests of building, construction and materials. To be able to reach A2 class fire resistivity, compound formulations have crucial importance to fulfill the requirement of EN 13501 -1 standard.

Compounding is a kind of process for preparing polymeric materials with a specific formulations by extruder/compounder in a way that mixing or and blending polymers, additives and inorganic materials in a molten state. A2 class fire resistive ACP core materials compounds can be produced by continuous compounding process via co-rotating or counter rotating twin-screw compounders, single screw compounders, co-kneaders or extruders. Besides that, Batch-wise production method with a banbury or an equipment similar to banbury can also be used for compounding process of A2 class fire resistive ACP core materials compounds. Present invention of this patent comprises of reprocess ability of said A2 class fire resistive ACP core materials compounds by an extrusion method coupled with a flat die or an equipment similar to flat die for ACP manufacturing.

In compounding process of ACP manufacturing at B1/B2 class fire resistivity of prior art, linear low density polyethylene (LLDPE), low density polyethylene(LDPE), mixture of them or recycled form of those polymers were used as carrier medium of flame-retardant materials. Besides using LDPE, LLDPE or mixtures of both, present invention of this patent proposed such thermoplastic resins as polymeric medium. This invention comprise using thermoplastic resins are polyoxymethylene (POM), polymeric form of ethylene vinyl acetate (EVA), polyamide 6 (PA 6), polyamide 6.6 (PA 6.6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate, (PMMA), polybuthyl acrylate (PBA), polystyrene (PS), polyolefin elastomers (POE), polycarbonate (PC), Ethylene-Propylene Rubber (EPR), Styrene- butadiene-styrene (SBS), Styrene-ethylene-butylene-Styrene (SEBS), ethylene-butyl acrylate copolymers (EBA), ethylene-ethyl acrylate copolymers (EEA) or mixtures of said thermoplastic resins in any variations. The invention of this patent comprise using thermoset polymers such as epoxies, unsaturated polyesters, and thermoplastic vulcanizates as well.

Present invention comprise of polymer type and mixtures of polymers take place in A2 class fire resistive compound formulation. Polymer type and mixtures of polymers amount can be wt. % of 6 to 20, more preferably wt. % 7 to 18, more preferably wt. % of polymer mixture can be about 8 to 15%.

Flame retardant materials are the any substance that by chemical or physical action reduces flammability of fuels or slows their rate of combustion. Magnesium dihydroxide or aluminum trihydroxide are the well-known flame retardant materials for ACP manufacturing. Even though halogen containing flame retardant flame retardant materials are available, their usage are limited due to global regulation. Therefore, halogen-containing flame retardant materials is out of scope of present invention.

Besides ATH or MDH usage, authors of this invention related with the usage of different flame retardant material such as calcium carbonate, magnesium carbonate, ammonium polyphosphate (APP), melamine and derivatives of melamine compounds and nitrogen/phosphor based compounds for fire resistivity.

Present invention comprise synergist such as zinc borate Zinc hydroxystannate, zinc stannate, and nanoclays are also be used to enhance fire resistivity of said A2 class fire resistive extrudable core material compounds.

Present invention comprise of MDH usage as flame retardant material in about 80 to 94 wt. %. Present invention comprise particle size of MDH varying from 0.5 to 3000 micrometer, more preferably from 1 to 2000 micrometer, more preferably 1 -1000 micrometer, more preferably from 1 to 100 micrometer.

Present invention comprise of ATH usage as flame retardant material in about 80 about 94 wt. %. Present invention comprise particle size of ATH varying from 0.5 to 3000 micrometer, more preferably from 1 to 2000 micrometer, more preferably 1 -1000 micrometer, more preferably from 1 to 100 micrometer.

Present invention comprise of magnesium carbonate usage as flame retardant material in about 80 to 94 wt. %. Present invention comprise particle size of magnesium carbonate varying from 0.5 to 3000 micrometer, more preferably from 1 to 2000 micrometer, more preferably 1 -1000 micrometer, more preferably from 1 to 100 micrometer.

Present invention comprise of calcium carbonate usage as flame retardant material in about 80 to 94 wt. %. Present invention comprise particle size of calcium carbonate varying from 0.5 to 3000 micrometer, more preferably from 1 to 2000 micrometer, more preferably 1 -1000 micrometer, more preferably from 1 to 100 micrometer.

Present invention comprise of APP usage as flame retardant material in about 80-94 wt. %. Present invention comprise particle size of APP varying from 0.5 to 50 micrometer.

Present invention comprise of usage of mixtures of ATH, MDH, Magnesium Carbonate, Calcium Carbonate and APP in any combinations of said materials as flame retardant material in about 80 to 94 wt. %. Present invention comprise particle size of flame-retardants varying from 0.5 to 3000 micrometer. Present invention comprise usage of Zinc borate Zinc hydroxystannate and zinc stannate, and nanoclays. The said synergists can be used in varying amount from 0,1 to 10 wt. %, more preferably from 1 to 7 w %, more preferably from 2 to 5 wt. %.

Present invention also comprise coupling agent usage in compounding formulation. Maleic anhydride grafted LLDPE (MAH-g-LLDPE), Maleic anhydride grafted PP (MAH-g-PP), Maleic anhydride grafted POE (MAH-g-POE), silane-coupling agents such as vinyl trimethoxysilane (VTMS), vinyl triethoxysilane (VTES), and amino propyl triethoxysilane (APTES) can be used to enhance compatibility of polymeric materials and inorganic materials. Present invention comprise using MAH-g-POE in A2 class fire resistive compound formulation. MAH-g-POE can be used at varying amount from 0,1 to 6 wt. %, more preferably from 0,5 to 4 wt. %, more preferably from 2 to 4 wt. %.

Present invention comprise usage of lubricants as well. Besides magnesium stearate, calcium stearate, polyethylene (PE) wax, EVA wax, polydimethyl siloxane (PDMS), PDMS-LLDPE, PDMS-PMMA, PDMS-PBA, PDMS-EBA, PDMS-EEA copolymers can be use as lubricant successfully.

As an example, at Present invention, PDMS can be used as lubricant in varying amount from 0,1 to 10 wt. %, more preferably from 0,5 to 8 wt. %, more preferably from 0,5 to 5 wt. %.

EXAMPLES

Table 2: Examples for Extrudable A2 Class Fire Resistive Core Material Compound for ACP

The formulations above are processed at banbury, co-kneader, single screw, co-rotating or counter-rotating twin-screw compounder line, then converted into pellet or granule form allowing to re-extrudable into desired shape by using a conventional extrusion coupled with flat die for manufacturing ACP. The compounds above can comply with specifications of A2 class fire resistivity of EN 13501 -1.

Claims

1 A process for the preparation of extrudable compound for aluminum composite panel at a2 class fire resistivity and method of making aluminum composite panel with thereof, in which said compound can be extrudable into a desired shape for manufacturing of aluminum-plastic composite panel (ACP) at A2 class fire resistivity according to Standard of EN 13501 -1 , said extrudable compounds comprises polymeric structures at wt. % of 6 to 20, more preferably wt. % 7 to 18, more preferably wt. % of polymer mixture can be about 8 to 15% and in which said polymeric structures comprises using thermoplastic resins polyoxymethylene (POM), polymeric form of ethylene vynilacetate (EVA), polyamide 6 (PA6), polyamide 6.6 (PA6.6), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polymethyl methacrylate, (PMMA), polybuthyl acrylate (PBA), polystyrene (PS), polyolefin elastomers (POE), polycarbonate (PC), Ethylene- Propylene Rubber (EPR), Styrene-butadiene-styrene (SBS), Styrene-ethylene-butylene- Styrene (SEBS), ethylene-butyl acrylate copolymers (EBA), ethylene-ethyl acrylate copolymers (EEA) or mixtures of said thermoplastic resins in any variations and thermoset polymers are epoxies, unsaturated polyesters, thermoplastic vulcanizates.

2 The process according to claim 1 , wherein thermoplastic polymeric structures have melt flow index about 0,5 to 800 g/10 min.

3- The process according to claim 1 , wherein the extrudable thermoplastic resin compound comprises flame retardant materials such as aluminum trihydroxide (ATH) Magnesium Dihydroxide, Calcium Carbonate, Magnesium Carbonate, Ammonium Polyphosphate (APP), melamine, derivatives of melamine and nitrogen/phosphor based materials for fire resistivity.

4 Flame retardant materials according to claim 3 in which particle dimension of the said flame retardant materials are about 0,5 to 3000 micrometer.

5- Flame retardant materials according to claim 3 in which usage of the said flame retardant materials is between about wt % of 80 to 94.

6 The extrudable thermoplastic resin compound according to claim 1 in which the said compound formulation can have synergists.

7 Synergists according to claim 6 in which Zinc borate, Zinc hydroxystannate, zinc stannate, and nanoclays can be used as synergist in varying amount from 0,1 to 10 wt. %, more preferably from 1 to 7 w %, more preferably from 2 to 5 wt. %.

8 The extrudable thermoplastic resin compound according to claim 1 in which the said compound formulation can have coupling agent in compounding formulation.

9 Coupling agents according to claim 10 in which maleic anhydride grafted LLDPE (MAH- g-LLDPE), maleic anhydride grafted PP (MAH-g-PP), maleic anhydride grafted POE (MAH-g-POE), silane coupling agents such as vinyl trimethoxysilane (VTMS), vinyl triethoxysilane (VTES), amino propyl trimethoxysilane (APTES) can be used to enhance compatibility of polymeric materials and inorganic materials in a varying amount between 0,1 to 6 wt. %, more preferably from 0,5 to 4 wt. %, more preferably from 2 to 4 wt. %. The extrudable thermoplastic resin compound according to claim 1 in which compound formulation can have lubricants.

Lubricants according to claim 10 in which magnesium stearate, calcium stearate, polyethylene (PE) wax, EVA wax, polydimethyl siloxane (PDMS), PDMS-LLDPE, PDMS- PMMA, PDMS-PBA, PDMS-EBA, PDMS-EEA copolymers can be use as lubricant at amount of between 0,1 to 10 wt. %, more preferably from 0,5 to 8 wt. %, more preferably from 0,5 to 5 wt. %.