WO1989001864A1 - Fire resistant insulation composition - Google Patents

Fire resistant insulation composition Download PDF

Info

Publication number
WO1989001864A1
WO1989001864A1 PCT/US1988/002911 US8802911W WO8901864A1 WO 1989001864 A1 WO1989001864 A1 WO 1989001864A1 US 8802911 W US8802911 W US 8802911W WO 8901864 A1 WO8901864 A1 WO 8901864A1
Authority
WO
WIPO (PCT)
Prior art keywords
fire resistant
tunnel
polyethylene foam
fire
steel sheet
Prior art date
Application number
PCT/US1988/002911
Other languages
French (fr)
Inventor
Ioannis Apostolopoulos
Original Assignee
The Dow Chemical Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Dow Chemical Company filed Critical The Dow Chemical Company
Priority to DE3853163T priority Critical patent/DE3853163T2/en
Priority to EP88908536A priority patent/EP0375738B1/en
Publication of WO1989001864A1 publication Critical patent/WO1989001864A1/en
Priority to FI900927A priority patent/FI99198C/en
Priority to NO900870A priority patent/NO175810C/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/18Layered products comprising a layer of metal comprising iron or steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • EFIXED CONSTRUCTIONS
    • E04BUILDING
    • E04BGENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92Protection against other undesired influences or dangers
    • E04B1/94Protection against other undesired influences or dangers against fire
    • EFIXED CONSTRUCTIONS
    • E21EARTH OR ROCK DRILLING; MINING
    • E21DSHAFTS; TUNNELS; GALLERIES; LARGE UNDERGROUND CHAMBERS
    • E21D11/00Lining tunnels, galleries or other underground cavities, e.g. large underground chambers; Linings therefor; Making such linings in situ, e.g. by assembling
    • E21D11/38Waterproofing; Heat insulating; Soundproofing; Electric insulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00Composition of foam
    • B32B2266/02Organic
    • B32B2266/0214Materials belonging to B32B27/00
    • B32B2266/025Polyolefin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00Composition of foam
    • B32B2266/08Closed cell foam
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/70Other properties
    • B32B2307/714Inert, i.e. inert to chemical degradation, corrosion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2311/00Metals, their alloys or their compounds
    • B32B2311/30Iron, e.g. steel
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00Buildings or parts thereof

Definitions

  • the insulation material Since the heat contained in the water is released upon exposure to the cold rock face and the cold exterior air, it follows that the volume of air between the rock surface and the insulation material should be kept to a minimum. It is therefore essential that the insulation material be flexible and to some extent capable of following the contours of the interior rock wall of the tunnel. In addition, the particular insulation material employed should have a very low heat conduction coefficient and at the same time be impervious to water. For economic reasons such a tunnel insulation material should also be easy to install and require little 35 maintenance.
  • Polyethylene foam has a low heat conductivity and absorbs a negligible amount of water, properties which it maintains at temperatures as low as ⁇ 40°C. It resists weathering and is strong enough to withstand slipstream pressures from wind, passing trucks or trains. It is resistant to minor mechanical damage "and the flexibility of this material enables it to conform to the blasted rock surfaces of interior tunnel walls. It can be readily fabricated and its light weight and workability make it easy to install within tunnel confines, see "Polyethylene Foam Insulation Solves Icing Problem in Rocky Mountain Railway Tunnels" Sally Woods, Engineering Digest, pp 13-16, August 1985.
  • polyethylene foams can be made flame retardant by the addition of fire retardant additives.
  • fire retardant additives contain halogenated, which release bromine and chlorine gases when burning. These gases are heavy and toxic and can be more hazardous than the fire itself in the case of a non-fire retardant treated foam.
  • a tunnel insulation material that has all of the advantages of polyethylene foam, including the insulation properties of polyethylene foam, but which is also fire resistant.
  • This invention relates to a fire resistant tunnel insulation material or composition. More particularly, this invention relates to a fire resistant tunnel composition comprising a closed cell m polyethylene foam that is bonded to a metal sheet. Still more particularly, this invention is related to a fire resistant insulating composition comprising a closed cell polyethylene foam that has been bonded to a ,,- metal sheet by means of an ethylene acrylic acid copolymer. The outside surface of the metal sheet is generally coated to prevent corrosion.
  • a second aspect of this invention relates to a 2 Q method of applying the fire resistant tunnel insulation of the present invention to the interior of a tunnel rock face wall.
  • Figure 1 is a cross sectional view of the fire - c resistant tunnel insulating composition of the present invention.
  • Figure 2 is a cross sectional view of a tunnel lined with the fire resistant tunnel insulating
  • the closest prior art known to applicant consists of a double lining of aluminum having a frost insulation material sandwiched between the aluminum sheets, see "Insulated Panels for Protection against Water and Frost", Krokeborg and Pedersen, Proceedings International Symposium, Oslo 1984, (TAPIR, Trondheim) .
  • the aluminum lining comprises essentially a heavy gauge foil, approximately 0.5 to 0.7 mm thick, which contains a mineral wool insulation in between the layers of aluminum foil.
  • Such an insulation material has the disadvantage of tearing easily on the rough surface of a tunnel rock face, thereby exposing the insulation material to the rock wall surface.
  • Mineral wool is not very suitable for use as a tunnel insulation material. ra Mineral wool rapidly absorbs water which subsequently freezes and destroys the insulation value of this material.
  • the aluminum foil layers melt at relatively low temperatures of approximately 660°C. In cases of a hot fire, the chances of the aluminum T5 melting and causing the insulation to collapse and destroy or short-circuit power lines is high.
  • Figure 1 discloses a cross-section of the fire resistant insulating composition.
  • the compositions of this invention have been especially developed as tunnel insulation materials, it should be clearly understood 5 that these compositions, or slightly modified versions thereof, can also be used wherever a fire resistant insulating composition is required.
  • wall insulations for buildings such as houses, -1 warehouses, factories, thermal roofing insulations, pipe insulations and reaction vessel insulations for temperatures ranging from ⁇ 40°C to 70°C are all contemplated to be within the scope of applicant's claimed invention.
  • any plastic foam material can be used as an insulating material in accordance with the practise of this invention as for example, polyurethane, poly ⁇ styrene, polyethylene, cross-linked polyethylene, polypropylene or pol vinylchloride.
  • a closed cell polyethylene foam represents the preferred insulation species of applicant's invention.
  • TX Closed cell polyethylene foams are conveniently available in the form of extruded planks that measure from 20 to 120 cm in width and from 0.2 to 5 meters in length. These planks are available in thicknesses of 5 30, 50, 70, 80 and 100 mm. The thickness of the particular planks that are employed is dependent upon the climate and the severity of winter conditions to which the tunnel is exposed. Normally, planks having a width of about 1 meter, a length of about 2 meters, and X1 having a thickness of about 50 mm are employed.
  • polyethylene foam material Inasmuch as this type of polyethylene foam material is constructed of millions of tiny closed cells, it has a high insulation capacity. It permits only negligible water or steam penetration, which makes it an excellent 5 barrier for ground water.
  • Polyethylene foam is sufficiently flexible and resilient so as to give and not tear on jagged rock wall surfaces.
  • polyethylene foams maintain their excellent properties 0 over a wide range of temperatures ranging from ⁇ 40°C to 70°C. Thus, they can be installed over a wide range of ambient temperatures and numerous tunnels have been successfully insulated with polyethylene foam to prevent ground water from freezing on tunnel wall surfaces.
  • polyethylene foam will burn when exposed to a naked flame for a short period of time.
  • fire retardant chemicals can be employed to make polyethylene foams more flame resistant.
  • these fire retardant additives generally contain halogen derivates that release toxic gases, such as bromine and chlorine, when burning. These toxic gases can be even more hazardous than the fire itself in a relatively confined area, such as, for example, in the middle of a long tunnel.
  • a composite material or polyethylene laminate has been developed in which the surface of the polyethylene foam facing the tunnel interior is covered by a metal surface.
  • the use of a metal sheet as a cover for combustible-materials is not new.
  • the bonding of a metal sheet to a plastic foam material to form a fire resistant insulating composition is deemed to be novel.
  • the metal surface or surfaces are bonded by means of a particular thermoplastic bonding agent or adhesive material that melts at approximately the same or at a higher temperature than that at which the polyethylene foam melts.
  • a particular thermoplastic bonding agent or adhesive material that melts at approximately the same or at a higher temperature than that at which the polyethylene foam melts.
  • non-ferrous metal sheets may be used for certain installations
  • the use of a steel sheet is preferred for the installation of fire resistant tunnel insulation materials.
  • the thickness of the steel sheet can be from about 0.01 to 0.3 mm, and preferably is from about 0.02 to 0.2 mm so as to be flexible.
  • the length and width of the steel sheet is controlled by the length and width of the polyethylene planks employed. If a composite containing only a single outer steel layer is employed, the steel layer should include about 50 mm of additional steel sheet which overlaps each edge of the polyethylene plank. This overlap can be folded over to cover the edges of the polyethylene plank so that no polyethylene surface is exposed to the interior surface of the tunnel.
  • the bonding agent or adhesive layer can be comprised of a variety of materials, as long as it adheres satisfactorily to the steel sheet and to the polyethylene foam. It should also melt at appproxi- mately the same or at a higher temperature than the polyethylene foam, in order to enable the polyethylene foam to melt and pull away from the hot metal sheet when exposed to a direct source of heat, instead of delaminating from the metal sheet. In case of a major tunnel fire, this enables the polyethylene foam to form s. liquid metal protected from an open flame by the steel layer. This melt can flow by gravity behind the steel layer into the ground drainage provided out of harm's way.
  • Suitable bonding agents include adhesive resins, such as ethylene vinyl alcohol and ethylene acrylic acid copolymer, with the latter being the adhesive resin of choice.
  • the adhesive resin can be directly applied to the steel sheet by extruding the
  • T0 molten resin onto the metal sheet through a die at temperatures of about 210°C.
  • the molten adhesive resin can be applied as a falling curtain directly onto the steel sheet as it passes continuously beneath the die
  • T5 opening The rate of speed at which the steel sheet travels determines the thickness of the adhesive coating.
  • the adhesive layer is solid and tack free so that, for example*, the adhesive-coated steel sheet can be rolled up into a 20) coil and stored for future use.
  • the steel sheet containing the adhesive layer can then be laminated to the polyethylene foam plank by means of a hot air lamination technique. Hot air at 25 about 150°C is blown directly against the adhesive- coated metal sheet to soften the adhesive layer. The softened, adhesive-coated steel sheet is firmly pressed against the polyethylene foam and cooled. Upon cooling the steel sheet remains firmly and flexibly bonded to
  • the polyethylene foam For polyethylene foam composites having two metal surface layers, the process of laminating the adhesive-coated steel sheet is repeated on the other side.
  • the application of the adhesive resin to the steel sheet, the hot air bonding of the softened resin to the polyethylene foam, and the subsequent cutting of the laminated planks to their desired length can all be combined into a continuous operation having a through-put of finished composite material, ranging from about 0.5 to 2.0 meters per minute.
  • the adhesive-coated steel sheets can be pre-prepared, stored, and subsequently bonded to the polyethylene foam as required.
  • the exterior surface of the steel sheet is generally coated to prevent the steel from corrosion.
  • one side of the steel sheet can be pre-coated with a protective coating, prior to the application of the adhesive resin on the opposite side. Any number of protective coatings or paint coatings known to those skilled in the art can be employed for this purpose.
  • a paint coating is employed which is both corrosion resistant and fire resistant.
  • a coating can be sprayed, brushed or rolled onto the metal sheet or onto the finished metal composite.
  • the fire resistant coating should be such that it will not propagate a fire once it is ignited. Preferably, it should be of the type that will extinguish itself within a few minutes after direct flame contact has been removed.
  • the paint composition should be flexible in order that no cracks or chipping of the paint coating will occur during handling and installation. Coatings that are chemically resistant to automobile exhaust gases, particularly sulfur dioxide, sulfur trioxide, nitrous oxides, carbon monoxide, carbon dioxide, and their corresponding acids are particularly desirable.
  • paint coatings comprising phenolic based resins, phenol-aldehyde resins, acrylic resins or epoxy resins.
  • Epoxy resin based paint coatings form the coating of choice. In addition to good adherence
  • Fire resistant tunnel insulating composite planks prepared in accordance with this invention, can
  • the polyethylene planks are joined at their long edges to form a mat.
  • the width of the mat is equal to the length of the composite planks.
  • the length of the 2U individual mats should be composed of a sufficient number of planks so as to cover a major portion, or the whole cross-section, of a tunnel wall and ceiling.
  • the composite planks are edge-joined by means of a thermoplastic hot melt adhesive, as for
  • a urethane elastomer for example, a urethane elastomer.
  • Such an adhesive is readily applied and retains sufficient flexibility, even in extreme hot or cold weather, so as not to crack or break during installation.
  • Mats formed in this fashion are fastened to the rock face wall by means of bolts that have been previously inserted into the rock face wall. Holes are drilled at right angles and the threaded bolts are inserted and permanently sealed in place by means of an epoxy resin. This serves to anchor the bolt in place and prevent ground water from leaking around each drilled hole.
  • the bolts are so arranged that each composite plank of a mat is independently fastened to the rock face wall, thereby preventing the collapse of individual composite planks in case of a failure of the adhesive.
  • Such composite mats can be prepared outside of the tunnel entrance and transferred to the mounting site by sky-lift mounting vehicles.
  • the mats are carefully centered and attached to the rock face tunnel wall by means of nuts and washer plates that are fastened onto the previously positioned bolts.
  • the washer plates are approximately 200 cm2 and have upturned edges so as not to scratch or cut into the treated fire resistant coating of the composite material.
  • This process of preparing and installing mats is repeated with as many mats being installed as are necessary in order to cover the interior surface of the tunnel.
  • the edges of each mat should overlap the edges of the adjacent mat from about 30 to 50 cm, so that absolutely no polyethylene foam is anywhere exposed to the interior surface of the tunnel. It is also important that no air circulate behind the mat to create drafts. Void spaces, including especially the portal edges of the mat, must be sealed by means of a fire resistant filler, such as mineral wool.
  • Example 1 illustrates the fire resistant properties of a polyethylene foam composite material in accordance with the present invention in comparison to the polyethylene foam of the prior art.
  • Panels of a closed cell polyethylene foam, a closed-cell polyethylene foam that has been treated so as to be fire resistant, a polyethylene foam composite that has been bonded to a steel sheet having a corrosion resistant and partially fire resistant coating on its exterior surface, and a polyethylene foam composite that has been bonded to a steel sheet having a corrosion and fire resistant coating on its : exterior surface are individually placed in an upright position.
  • a Bunsen burner is inclined at a 45°C angle and placed so that the flame is in direct contact with a spot located about 5 cm from the base of each test panel. At the hottest point of flame attack, temperatures of 900 to 920°C are recorded by means of a technoterm 9500 thermometer.
  • All of the samples comprise a closed cell polyethylene extruded foam having dimensions of 25 cm in width, 30 cm in length and 5 cm in thickness.
  • the polyethylene foam composite is coated with two different corrosion resistant epoxy coatings: (1) a corrosion resistant coating having fire retardant properties, and (2) a corrosion resistant coating having improved fire retardant properties.
  • the composition of these corrosion resistant coatings are as follows:
  • the viscosities of the final compositions can be adjusted with additional solvent to permit the type of application desired, i.e., spraying, brushing or rolling. -

Landscapes

  • Engineering & Computer Science (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Mining & Mineral Resources (AREA)
  • Civil Engineering (AREA)
  • Geology (AREA)
  • Electromagnetism (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Physics & Mathematics (AREA)
  • Insulated Conductors (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Glass Compositions (AREA)
  • Building Environments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Percussion Or Vibration Massage (AREA)
  • Lining And Supports For Tunnels (AREA)
  • Inorganic Insulating Materials (AREA)

Abstract

A fire resistant insulating composite material is described which can be used to insulate tunnel walls and prevent ground water from freezing. This composite material comprises a layer of closed cell polyethylene foam that has been bonded on one or both sides to a metal sheet. Another aspect of the invention relates to the installation of such fire resistant tunnel insulating compositions to the interior rock face wall of a tunnel.

Description

FIRE RESISTANT INSULATION COMPOSITION
One of the problems frequently encountered in tunnels that are situated in areas subject to severe frost is the problem of ground water. Problems arise
5 due to the fact that water leaks into the interior of the tunnel via a natural network of cracks and fissures and does not freeze dry. In winter when the temperature falls below 0°C, this continuous flow of water freezes and gradually builds up large ice columns that cover T the walls and form massive icicles that are suspended from the ceiling, generally at or near the portal entrances. Even at temperatures that are slightly above freezing, differences in barometric pressures at each portal gives rise to a venturi effect in which
T5 strong cold winds sometimes result in a build-up of massive ice formations at the entrances of tunnels.
The formation of ice along tunnel walls and ditches often blocks drainage, causing water to spill α onto the road or railroad track bed where it freezes. Driving becomes dangerous and the roadbeds, or tracks in the case of railroad tunnels, are difficult to maintain, especially in busy tunnels. In serious cases 5- massive ice columns or icicle formations on tunnel roofs can cause tremendous loads pulling down electrical wires and support brackets causing serious hazards, particularly during periods of thaw.
Different methods have been employed to deal with these problems. Maintenance crews can be employed to hammer and chip away the ice, or to spray the ice with salt solutions. Such methods are costly in that they require the use of a large amount of manpower and cause corrosion or damage to the ecology. Alternatively, attempts to seal the cracks in tunnel walls by injecting chemicals or by caulking with sprayed concrete have also been employed. These methods are complicated, expensive, and to a large extent the results are uncertain. If one manages to establish a water-tight screen around a part or section of the tunnel, frequently the water pressure gradually builds up only to seep through somewhere else, in many cases adjacent to the cracks that have just been filled.
One of the simplest approaches to this problem' is to utilize the warmth of the mountain interior in order to prevent the ground water from freezing. Thus, by maintaining the temperature of the ground water above freezing, it will drain normally into the drainage provided, thereby preventing damage to the tunnel interior caused by ground water freezing. This can be effectively accomplished by insulating the surface walls and ceiling of the tunnel interior.
Since the heat contained in the water is released upon exposure to the cold rock face and the cold exterior air, it follows that the volume of air between the rock surface and the insulation material should be kept to a minimum. It is therefore essential that the insulation material be flexible and to some extent capable of following the contours of the interior rock wall of the tunnel. In addition, the particular insulation material employed should have a very low heat conduction coefficient and at the same time be impervious to water. For economic reasons such a tunnel insulation material should also be easy to install and require little 35 maintenance.
One of the best insulation materials, that has proved most successful in solving tunnel icing problems of this type, is an extruded closed cell polyethylene foam. Polyethylene foam has a low heat conductivity and absorbs a negligible amount of water, properties which it maintains at temperatures as low as ~40°C. It resists weathering and is strong enough to withstand slipstream pressures from wind, passing trucks or trains. It is resistant to minor mechanical damage "and the flexibility of this material enables it to conform to the blasted rock surfaces of interior tunnel walls. It can be readily fabricated and its light weight and workability make it easy to install within tunnel confines, see "Polyethylene Foam Insulation Solves Icing Problem in Rocky Mountain Railway Tunnels" Sally Woods, Engineering Digest, pp 13-16, August 1985.
One disadvantage, however, to the use of polyethylene foam is its flammability. Polyethylene foams can be made flame retardant by the addition of fire retardant additives. Generally, however, such fire retardant additives contain halogenated, which release bromine and chlorine gases when burning. These gases are heavy and toxic and can be more hazardous than the fire itself in the case of a non-fire retardant treated foam. Thus, there is a need for a tunnel insulation material that has all of the advantages of polyethylene foam, including the insulation properties of polyethylene foam, but which is also fire resistant.
This invention relates to a fire resistant tunnel insulation material or composition. More particularly, this invention relates to a fire resistant tunnel composition comprising a closed cell m polyethylene foam that is bonded to a metal sheet. Still more particularly, this invention is related to a fire resistant insulating composition comprising a closed cell polyethylene foam that has been bonded to a ,,- metal sheet by means of an ethylene acrylic acid copolymer. The outside surface of the metal sheet is generally coated to prevent corrosion.
A second aspect of this invention relates to a 2Q method of applying the fire resistant tunnel insulation of the present invention to the interior of a tunnel rock face wall.
Figure 1 is a cross sectional view of the fire -c resistant tunnel insulating composition of the present invention.
Figure 2 is a cross sectional view of a tunnel lined with the fire resistant tunnel insulating
30 composition of the present invention.
The closest prior art known to applicant consists of a double lining of aluminum having a frost insulation material sandwiched between the aluminum sheets, see "Insulated Panels for Protection Against Water and Frost", Krokeborg and Pedersen, Proceedings International Symposium, Oslo 1984, (TAPIR, Trondheim) . The aluminum lining comprises essentially a heavy gauge foil, approximately 0.5 to 0.7 mm thick, which contains a mineral wool insulation in between the layers of aluminum foil. Such an insulation material has the disadvantage of tearing easily on the rough surface of a tunnel rock face, thereby exposing the insulation material to the rock wall surface. Mineral wool is not very suitable for use as a tunnel insulation material. ra Mineral wool rapidly absorbs water which subsequently freezes and destroys the insulation value of this material. Additionally, the aluminum foil layers melt at relatively low temperatures of approximately 660°C. In cases of a hot fire, the chances of the aluminum T5 melting and causing the insulation to collapse and destroy or short-circuit power lines is high.
These problems can be overcome by utilizing the fire resistant tunnel insulation compositions of this 0: invention. Referring to the drawings, Figure 1 discloses a cross-section of the fire resistant insulating composition. Although the compositions of this invention have been especially developed as tunnel insulation materials, it should be clearly understood 5 that these compositions, or slightly modified versions thereof, can also be used wherever a fire resistant insulating composition is required. Thus, for example, wall insulations for buildings such as houses, -1 warehouses, factories, thermal roofing insulations, pipe insulations and reaction vessel insulations for temperatures ranging from ~40°C to 70°C are all contemplated to be within the scope of applicant's claimed invention. Any plastic foam material can be used as an insulating material in accordance with the practise of this invention as for example, polyurethane, poly¬ styrene, polyethylene, cross-linked polyethylene, polypropylene or pol vinylchloride. In view of the superior insulation properties and the resistance to water absorption, a closed cell polyethylene foam represents the preferred insulation species of applicant's invention. TX Closed cell polyethylene foams are conveniently available in the form of extruded planks that measure from 20 to 120 cm in width and from 0.2 to 5 meters in length. These planks are available in thicknesses of 5 30, 50, 70, 80 and 100 mm. The thickness of the particular planks that are employed is dependent upon the climate and the severity of winter conditions to which the tunnel is exposed. Normally, planks having a width of about 1 meter, a length of about 2 meters, and X1 having a thickness of about 50 mm are employed.
Inasmuch as this type of polyethylene foam material is constructed of millions of tiny closed cells, it has a high insulation capacity. It permits only negligible water or steam penetration, which makes it an excellent 5 barrier for ground water. Polyethylene foam is sufficiently flexible and resilient so as to give and not tear on jagged rock wall surfaces. Moreover, polyethylene foams maintain their excellent properties 0 over a wide range of temperatures ranging from ~40°C to 70°C. Thus, they can be installed over a wide range of ambient temperatures and numerous tunnels have been successfully insulated with polyethylene foam to prevent ground water from freezing on tunnel wall surfaces. However, as with all thermoplastic foam materials, polyethylene foam will burn when exposed to a naked flame for a short period of time. Moreover, when large amounts of polyethylene foam burn, dense clouds of smoke are produced. The addition of fire retardant chemicals can be employed to make polyethylene foams more flame resistant. However, as indicated, these fire retardant additives generally contain halogen derivates that release toxic gases, such as bromine and chlorine, when burning. These toxic gases can be even more hazardous than the fire itself in a relatively confined area, such as, for example, in the middle of a long tunnel.
In order to avoid open flames from coming into direct contact with the polyethylene foam, a composite material or polyethylene laminate has been developed in which the surface of the polyethylene foam facing the tunnel interior is covered by a metal surface. The use of a metal sheet as a cover for combustible-materials is not new. However, the bonding of a metal sheet to a plastic foam material to form a fire resistant insulating composition is deemed to be novel. In some applications, it may be desirable to cover both surfaces of the polyethylene foam with a metal sheet, thereby forming a composite of polyethylene foam between two metal surface layers.
In accordance with the teachings of this invention, the metal surface or surfaces are bonded by means of a particular thermoplastic bonding agent or adhesive material that melts at approximately the same or at a higher temperature than that at which the polyethylene foam melts. Thus, laboratory tests have shown that when an exposed flame comes in direct contact with the surface of the composite metal sheet, the polyethylene foam does not de-laminate due to poor adhesion. Moreover, the polyethylene foam tends to shrink or melt away from the source of heat to form cavities or pockets behind the metal sheet, thereby minimizing the formation of drafts and subsequent burning.
Whereas non-ferrous metal sheets may be used for certain installations, the use of a steel sheet is preferred for the installation of fire resistant tunnel insulation materials. The thickness of the steel sheet can be from about 0.01 to 0.3 mm, and preferably is from about 0.02 to 0.2 mm so as to be flexible.
The length and width of the steel sheet is controlled by the length and width of the polyethylene planks employed. If a composite containing only a single outer steel layer is employed, the steel layer should include about 50 mm of additional steel sheet which overlaps each edge of the polyethylene plank. This overlap can be folded over to cover the edges of the polyethylene plank so that no polyethylene surface is exposed to the interior surface of the tunnel.
The bonding agent or adhesive layer can be comprised of a variety of materials, as long as it adheres satisfactorily to the steel sheet and to the polyethylene foam. It should also melt at appproxi- mately the same or at a higher temperature than the polyethylene foam, in order to enable the polyethylene foam to melt and pull away from the hot metal sheet when exposed to a direct source of heat, instead of delaminating from the metal sheet. In case of a major tunnel fire, this enables the polyethylene foam to form s. liquid metal protected from an open flame by the steel layer. This melt can flow by gravity behind the steel layer into the ground drainage provided out of harm's way.
Suitable bonding agents include adhesive resins, such as ethylene vinyl alcohol and ethylene acrylic acid copolymer, with the latter being the adhesive resin of choice. The adhesive resin can be directly applied to the steel sheet by extruding the
T0 molten resin onto the metal sheet through a die at temperatures of about 210°C. The molten adhesive resin can be applied as a falling curtain directly onto the steel sheet as it passes continuously beneath the die
T5 opening. The rate of speed at which the steel sheet travels determines the thickness of the adhesive coating. At ambient temperatures, the adhesive layer is solid and tack free so that, for example*, the adhesive-coated steel sheet can be rolled up into a 20) coil and stored for future use.
The steel sheet containing the adhesive layer can then be laminated to the polyethylene foam plank by means of a hot air lamination technique. Hot air at 25 about 150°C is blown directly against the adhesive- coated metal sheet to soften the adhesive layer. The softened, adhesive-coated steel sheet is firmly pressed against the polyethylene foam and cooled. Upon cooling the steel sheet remains firmly and flexibly bonded to
30= the polyethylene foam. For polyethylene foam composites having two metal surface layers, the process of laminating the adhesive-coated steel sheet is repeated on the other side. The application of the adhesive resin to the steel sheet, the hot air bonding of the softened resin to the polyethylene foam, and the subsequent cutting of the laminated planks to their desired length can all be combined into a continuous operation having a through-put of finished composite material, ranging from about 0.5 to 2.0 meters per minute. Alternatively, the adhesive-coated steel sheets can be pre-prepared, stored, and subsequently bonded to the polyethylene foam as required.
Following the bonding of the steel sheets onto the polyethylene foam board, the exterior surface of the steel sheet is generally coated to prevent the steel from corrosion. Alternatively, one side of the steel sheet can be pre-coated with a protective coating, prior to the application of the adhesive resin on the opposite side. Any number of protective coatings or paint coatings known to those skilled in the art can be employed for this purpose.
Preferably, a paint coating is employed which is both corrosion resistant and fire resistant. Such a coating can be sprayed, brushed or rolled onto the metal sheet or onto the finished metal composite. The fire resistant coating should be such that it will not propagate a fire once it is ignited. Preferably, it should be of the type that will extinguish itself within a few minutes after direct flame contact has been removed. The paint composition should be flexible in order that no cracks or chipping of the paint coating will occur during handling and installation. Coatings that are chemically resistant to automobile exhaust gases, particularly sulfur dioxide, sulfur trioxide, nitrous oxides, carbon monoxide, carbon dioxide, and their corresponding acids are particularly desirable. Illustrative of the paint coatings that may be employed are coating compositions comprising phenolic based resins, phenol-aldehyde resins, acrylic resins or epoxy resins. Epoxy resin based paint coatings form the coating of choice. In addition to good adherence
5 they provide excellent corrosion resistant properties and can be formulated to impart varying degrees of fire resistance. Additionally, such film coatings can be made sufficiently elastic so as to prevent cracking and
Tffi chipping of the coating during handling and installation.
Fire resistant tunnel insulating composite planks, prepared in accordance with this invention, can
15 be installed using simple techniques known to those skilled in the art. Thus, as seen in Figure 2, the polyethylene planks are joined at their long edges to form a mat. The width of the mat is equal to the length of the composite planks. The length of the 2U individual mats should be composed of a sufficient number of planks so as to cover a major portion, or the whole cross-section, of a tunnel wall and ceiling. Preferable", the composite planks are edge-joined by means of a thermoplastic hot melt adhesive, as for
25 example, a urethane elastomer. Such an adhesive is readily applied and retains sufficient flexibility, even in extreme hot or cold weather, so as not to crack or break during installation.
30) Mats formed in this fashion are fastened to the rock face wall by means of bolts that have been previously inserted into the rock face wall. Holes are drilled at right angles and the threaded bolts are inserted and permanently sealed in place by means of an epoxy resin. This serves to anchor the bolt in place and prevent ground water from leaking around each drilled hole. The bolts are so arranged that each composite plank of a mat is independently fastened to the rock face wall, thereby preventing the collapse of individual composite planks in case of a failure of the adhesive.
Such composite mats can be prepared outside of the tunnel entrance and transferred to the mounting site by sky-lift mounting vehicles. The mats are carefully centered and attached to the rock face tunnel wall by means of nuts and washer plates that are fastened onto the previously positioned bolts. The washer plates are approximately 200 cm2 and have upturned edges so as not to scratch or cut into the treated fire resistant coating of the composite material. This process of preparing and installing mats is repeated with as many mats being installed as are necessary in order to cover the interior surface of the tunnel. The edges of each mat should overlap the edges of the adjacent mat from about 30 to 50 cm, so that absolutely no polyethylene foam is anywhere exposed to the interior surface of the tunnel. It is also important that no air circulate behind the mat to create drafts. Void spaces, including especially the portal edges of the mat, must be sealed by means of a fire resistant filler, such as mineral wool.
The following Example illustrates the fire resistant properties of a polyethylene foam composite material in accordance with the present invention in comparison to the polyethylene foam of the prior art. EXAMPLE
Panels of a closed cell polyethylene foam, a closed-cell polyethylene foam that has been treated so as to be fire resistant, a polyethylene foam composite that has been bonded to a steel sheet having a corrosion resistant and partially fire resistant coating on its exterior surface, and a polyethylene foam composite that has been bonded to a steel sheet having a corrosion and fire resistant coating on its : exterior surface are individually placed in an upright position. A Bunsen burner is inclined at a 45°C angle and placed so that the flame is in direct contact with a spot located about 5 cm from the base of each test panel. At the hottest point of flame attack, temperatures of 900 to 920°C are recorded by means of a technoterm 9500 thermometer.
All of the samples comprise a closed cell polyethylene extruded foam having dimensions of 25 cm in width, 30 cm in length and 5 cm in thickness. The polyethylene foam composite is coated with two different corrosion resistant epoxy coatings: (1) a corrosion resistant coating having fire retardant properties, and (2) a corrosion resistant coating having improved fire retardant properties. The composition of these corrosion resistant coatings are as follows:
Composition (1)
(a) A high bromine (20-21 percent ), low molecular weight epoxy resin in an acetone solution (80 percent solids), having an epoxide equivalent weight of 480 to 560 based on resin solids;
100 parts
(b) A high molecular weight polyamide hardener having a weight average molecular weight of 285,000. 52 parts
Composition (2)
(a) A low molecular weight solid brominated epoxy resin having an epoxide equivalent weight of 440 to 470, a softening point of 78-85°C and a bromine content of 47 to 51 percent by weight; 80 parts
(b) A low molecular weight epoxy resin in a xylene solution (75 percent solids) having an epoxide equivalent weight of 435 to 550 based on resin solids and a softening point of 71 to 84°C; 20 parts
(c) A high molecular weight polyamide hardener having a weight average molecular weight of 285,000. 52 parts
The viscosities of the final compositions can be adjusted with additional solvent to permit the type of application desired, i.e., spraying, brushing or rolling. -
Table I describes the nature of the test samples prepared and the results obtained. TABLE I
Figure imgf000017_0001
Figure imgf000017_0002
0
5
Figure imgf000017_0003
0
* average of two samples Comments: Sample 1 - Active burning of a pool of molten foam remaining - fire had to be extinguished.
Sample 2 - Large hole in test sample where the foam melted and burned - fire self- extinguished after removal of open flame.
Sample 3 - Metal coating scorched but remained intact. Polyethylene foam withdrew
10 and melted away from point of hottest flame. No burning of any foam.
Sample 4 - Same as Sample 3.
T5
0
25:

Claims

C AIMS
1. A fire resistant tunnel insulating composition for use in lining tunnels comprising a closed cell polyethylene foam bonded to a metal sheet.
2. A fire resistant tunnel insulating composition according to Claim 1 wherein the metal sheet is a steel sheet of from 0.01 mm to 0.2 mm in
5 thickness.
3. A fire resistant tunnel insulation composition according to Claim 2 wherein the closed cell polyethylene foam is bonded on both sides to said
TO; steel sheet.
4. A fire resistant tunnel insulation composition according to Claim 2 wherein the polyethylene foam is bonded to said steel sheet by
15 means of an ethylene acrylic acid copolymer.
5. A fire resistant tunnel insulating composition according to Claims 2 or 3, further comprising a corrosion resistant coating on the outside
20; surface of said steel sheet.
6. A fire resistant tunnel insulation composition according to Claim 4 wherein the corrosion resistant coating is ethylene acrylic acid copolymer.
25.
7. A fire resistant tunnel insulating composition comprising a closed-cell polyethylene foam, a bonding agent, a steel sheet having a thickness of from 0.01 mm to 0.2 mm, and a fire and corrosion resistant coating on the outside surface of said steel sheet.
8. A fire resistant composition according to Claim 7 wherein the bonding agent is an ethylene acrylic acid copolymer and the fire and corrosion O' resistant coating is an epoxy resin coating.
9. A method of applying a fire resistant tunnel insulating composition of Claims 1-8 to the interior of a tunnel which comprises: 5 a) Preparing said fire resistant tunnel insulating compositions in the form of planks having dimensions in width of from 20 to 120 cm and in length of from 0.2 to ΣL 5 m;
b) joining the long edges of said planks together to form a mat;
c) inserting and anchoring bolts into the 5 tunnel rock face ceiling and walls, and
d) fastening said mat to said bolts.
10. A process according to Claim 9 wherein the D edges of said planks are joined by means of a hot melt glue.
PCT/US1988/002911 1987-08-26 1988-08-24 Fire resistant insulation composition WO1989001864A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
DE3853163T DE3853163T2 (en) 1987-08-26 1988-08-24 FIRE RESISTANT INSULATION COMPOSITION.
EP88908536A EP0375738B1 (en) 1987-08-26 1988-08-24 Fire resistant insulation composition
FI900927A FI99198C (en) 1987-08-26 1990-02-23 Refractory insulation composition and its use
NO900870A NO175810C (en) 1987-08-26 1990-02-23 Fire-resistant insulation composition for use in lining tunnels

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8720142 1987-08-26
GB878720142A GB8720142D0 (en) 1987-08-26 1987-08-26 Fire resistant insulation composition

Publications (1)

Publication Number Publication Date
WO1989001864A1 true WO1989001864A1 (en) 1989-03-09

Family

ID=10622844

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/002911 WO1989001864A1 (en) 1987-08-26 1988-08-24 Fire resistant insulation composition

Country Status (8)

Country Link
EP (1) EP0375738B1 (en)
JP (1) JP2698991B2 (en)
AT (1) ATE118732T1 (en)
DE (1) DE3853163T2 (en)
FI (1) FI99198C (en)
GB (1) GB8720142D0 (en)
NO (1) NO175810C (en)
WO (1) WO1989001864A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0424793A2 (en) * 1989-10-27 1991-05-02 General Electric Company Flame retardant low density extruded foam articles
EP0727548A1 (en) * 1995-02-15 1996-08-21 Servicios Carlos Y Alfonso, S.L. Procedure for the application of protection coating on walls, pillars and similar surfaces
ES2118035A1 (en) * 1996-03-18 1998-09-01 Construcciones Aplicaciones Y Covering sheet
FR2770448A1 (en) * 1997-11-06 1999-05-07 Euramax Coated Products Sa Composite metal and plastic panel, used in buildings and signs
FR2779802A1 (en) * 1998-06-16 1999-12-17 Paul Riedel Thermal isolating material in honeycombed flame resistant plastic material
WO2002053367A1 (en) * 2000-12-28 2002-07-11 Fernando Gordun Burillo Waterproofing sheet
ES2301412A1 (en) * 1996-03-18 2008-06-16 Construcciones, Aplicaciones Y Refuerzos S.A. Covering sheet

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10162322A1 (en) * 2001-12-19 2003-07-10 Fagerdala World Foams Ab Gusta Foamed heat insulation material, e.g. for tunnel lining, is built up of joined extruded sheets and contains aluminum flakes

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161561A (en) * 1977-03-05 1979-07-17 Firma Carl Freudenberg Multilayer plate
US4310587A (en) * 1980-03-11 1982-01-12 King-Seeley Thermos Company Fire resistant vapor barrier
JPS5756249A (en) * 1980-09-22 1982-04-03 Asahi Dow Ltd Laminate, principal ingredient thereof is polyolefin foaming body, and its manufacture

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3466222A (en) * 1967-07-26 1969-09-09 Lexsuco Inc Fire retardant insulative structure and roof deck construction comprising the same
FR2137235A1 (en) * 1971-05-17 1972-12-29 Ethyl Corp Plastic coated foamed metal (aluminium) panels
FR2230980B1 (en) * 1973-05-22 1976-04-23 Stop Sa
US3874983A (en) * 1973-12-17 1975-04-01 Dow Chemical Co Laminate construction
CH585828A5 (en) * 1974-02-27 1977-03-15 Alusuisse
JPS55171530U (en) * 1979-05-28 1980-12-09
JPS5894600A (en) * 1981-12-01 1983-06-04 東洋物産株式会社 Water-proof heat insulating plate and prevention of freezing of tunnel by using same
ES537709A0 (en) * 1984-11-16 1985-08-16 Gordun Burillo Fernando A SURFACE WATERPROOFING PROCEDURE, OF SPECIAL APPLICATION TO INTERIOR SURFACES OF TUNNELS, CHANNELS AND MINING

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161561A (en) * 1977-03-05 1979-07-17 Firma Carl Freudenberg Multilayer plate
US4310587A (en) * 1980-03-11 1982-01-12 King-Seeley Thermos Company Fire resistant vapor barrier
JPS5756249A (en) * 1980-09-22 1982-04-03 Asahi Dow Ltd Laminate, principal ingredient thereof is polyolefin foaming body, and its manufacture

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0424793A2 (en) * 1989-10-27 1991-05-02 General Electric Company Flame retardant low density extruded foam articles
EP0424793A3 (en) * 1989-10-27 1991-09-25 General Electric Company Flame retardant low density extruded foam articles
EP0727548A1 (en) * 1995-02-15 1996-08-21 Servicios Carlos Y Alfonso, S.L. Procedure for the application of protection coating on walls, pillars and similar surfaces
ES2118035A1 (en) * 1996-03-18 1998-09-01 Construcciones Aplicaciones Y Covering sheet
ES2301412A1 (en) * 1996-03-18 2008-06-16 Construcciones, Aplicaciones Y Refuerzos S.A. Covering sheet
FR2770448A1 (en) * 1997-11-06 1999-05-07 Euramax Coated Products Sa Composite metal and plastic panel, used in buildings and signs
FR2779802A1 (en) * 1998-06-16 1999-12-17 Paul Riedel Thermal isolating material in honeycombed flame resistant plastic material
WO2002053367A1 (en) * 2000-12-28 2002-07-11 Fernando Gordun Burillo Waterproofing sheet
ES2178587A1 (en) * 2000-12-28 2002-12-16 Burillo Fernando Gordun Waterproofing sheet

Also Published As

Publication number Publication date
EP0375738A1 (en) 1990-07-04
EP0375738A4 (en) 1990-09-05
GB8720142D0 (en) 1987-09-30
NO175810B (en) 1994-09-05
FI99198B (en) 1997-07-15
ATE118732T1 (en) 1995-03-15
NO900870L (en) 1990-04-23
JP2698991B2 (en) 1998-01-19
DE3853163T2 (en) 1995-06-22
NO175810C (en) 1994-12-14
DE3853163D1 (en) 1995-03-30
JPH03500030A (en) 1991-01-10
FI99198C (en) 1997-10-27
NO900870D0 (en) 1990-02-23
EP0375738B1 (en) 1995-02-22
FI900927A0 (en) 1990-02-23

Similar Documents

Publication Publication Date Title
US4719723A (en) Thermally efficient, protected membrane roofing system
US4651494A (en) Insulation panel for a roofing system or the like
US4492064A (en) Insulated roof construction
US3466222A (en) Fire retardant insulative structure and roof deck construction comprising the same
US4747247A (en) Roof system
EP0375738B1 (en) Fire resistant insulation composition
US4226071A (en) Method for the preparation of low temperature structure
EP0293381B1 (en) System for the insulation of mining installations and a method for implementing the system
Sandegren Insulation against ice railroad tunnels
CA1171776A (en) Composite insulating article for thermal and/or acoustic insulation
KR200483829Y1 (en) Sliding protection material improved anti-condensation and heat insulation effect
CN217840370U (en) Structure suitable for assembled ultralow energy consumption building outer wall through wire
JP2825829B2 (en) Snow melting roof structure
Guyer et al. An Introduction to Roofing Systems
JPH0527597Y2 (en)
Aamot et al. Protected membrane roofs in cold regions
RU2117121C1 (en) Method for increasing fire- and explosion-safety of roof coverings, and construction of roofing
Bast et al. Forensic Evaluation and Repair of Failures in 41-Story Granite Façade
Janopaul The use of polyurethane foam to provide a watertight concrete masonry wall and a sealed connection of the wall to the foundation
JPH1018447A (en) Method for connecting resin panels to each other
GB1600295A (en) Roofing
WATERPROOFING SECTION 07 13 00 SHEET MEMBRANE WATERPROOFING
JPS5833700A (en) Prevention of water leakage and freezing of tunnel
Luzik Protection of aluminum overcast constructions against fire
Guyer et al. Introduction to roofing systems

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): FI JP NO

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1988908536

Country of ref document: EP

Ref document number: 900927

Country of ref document: FI

WWP Wipo information: published in national office

Ref document number: 1988908536

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1988908536

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 900927

Country of ref document: FI