(19)
(11) EP 1 147 719 B1

(12) EUROPEAN PATENT SPECIFICATION

(45) Mention of the grant of the patent:
26.02.2003 Bulletin 2003/09

(21) Application number: 99928269.2

(22) Date of filing: 10.06.1999
(51) International Patent Classification (IPC)7A41D 31/00, A62B 17/00, B32B 5/18, B23B 27/06
(86) International application number:
PCT/RU9900/195
(87) International publication number:
WO 0000/9213 (24.02.2000 Gazette 2000/08)

(54)

HEAT RESISTANT FIREPROOF MATERIAL AND VARIANTS

HITZEBESTÄNDIGES, FLAMMHEMMENDES MATERIAL UND VARIANTEN

MATERIAU IGNIFUGE PROTEGEANT CONTRE LA CHALEUR ET VARIANTES


(84) Designated Contracting States:
DE FR GB IT SE

(30) Priority: 31.07.1998 RU 98114006

(43) Date of publication of application:
24.10.2001 Bulletin 2001/43

(73) Proprietors:
  • Aoot Nauchno- Issledovatelsky Institut Elastomernykh Materialov I Izdely
    Moscow, 119868 (RU)
  • Zakrytoe Aktsionernoe Obschestvo Nauchno-Tekhnichesky Tsentr "Vladipor"
    Vladimir, 600016 (RU)

(72) Inventors:
  • REZNICHENKO, Sergei Vladimirovich
    Moscow, 117049 (RU)
  • DUBYAGA, Vladimir Pavlovich
    Vladimir, 600020 (RU)
  • PUZDRASHONKOVA, Tamara Ivanovna
    Moscow, 105043 (RU)
  • BESFAMILNY, Igor Borisovich
    129085 Moscow (RU)
  • KARACHEVTSEV, Vyacheslav Grigorevich
    Vladimir, 600017 (RU)
  • LOGINOV, Vladimir Ivanovich
    Moscow, 129224 (RU)
  • ZUBOV, Alexei Leonidovich
    Moscow, 149172 (RU)
  • LARIONOV, Viktor Fedorovich
    Moscow, 129327 (RU)
  • VDOVIN, Pavel Albertovich
    Vladimir, 600009 (RU)
  • IGNATIEV, Dmitry Petrovich
    Moscow, 119569 (RU)

(74) Representative: Zellentin, Rüdiger et al
Patentanwälte Zellentin & Partner Zweibrückenstrasse 15
80331 München
80331 München (DE)


(56) References cited: : 
EP-A1- 0 108 865
DE-A1- 3 604 726
DE-A1- 4 010 038
US-A- 2 703 772
US-A- 4 250 223
WO-A-96/32252
DE-A1- 3 829 501
RU-C1- 2 105 580
US-A- 4 032 681
US-A- 5 656 355
   
       
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    Field of the Invention



    [0001] The invention relates to multilayer protective materials used to sew clothes for firemen and rescue workers operating in areas of high temperature and open fire. The invention may be used in the manufacture of other articles, such as capes, covers, and blankets, which must show increased heat resistance for operation in areas of intense heat radiation and also open fire during fire suppression, including the suppression of burning sources of oil, gas and other substances.

    Background Art



    [0002] In order to make protective clothes for firemen operating in areas of high temperatures and open fire, materials have been developed which are multilayer constructions comprising layers of heat-resistant fibers, hermetic and heat-reflecting polymeric and metal-polymeric layers. The known materials do not let water, which falls on the clothes in the process of extinguishing fires, pass through, but they are also impermeable in respect to moisture vapors released by the human body, and this creates difficult working conditions for the firemen.

    [0003] Protective clothes made from fire-resistant materials should provide certain comfort when work is being carried on in an emergency area: they should be elastic, sufficiently light, so that they would not constrain movement, be heat-reflective to such a degree that the temperature in the under-the-clothes area would not exceed the value at which a heat stroke may occur, i.e. not be more than 50°C, preferably not more than 30-35°C.

    [0004] A fire-resistant material is known which is made by joining a metallized polyethylene terephthalate film to a cloth of hollow nonprofiled threads, which are partially filled with air (Patent RU No. 2008044, A 62 B 17/00, 1994).

    [0005] A drawback of the known material is its instability when it falls into an open fire, during a sudden increase of a flow of heat, i.e. the polyethylene terephthalate film melts, baring the cloth, and is subjected to thermal destruction, this affecting the properties of the metal coating: it warps, exfoliates, as a result of which the heat-resistant properties of the clothes are impaired.

    [0006] A heat-reflecting material is known, which comprises a fibrous layer in the form of cloth of heat-resistant material on which a layer of hermetic material, made of filled fluorine-containing rubber, is applied. The latter is joined to a heat-reflecting layer made of one of the metals: aluminum, nickel, chromium, applied by the vacuum deposition method. The layer of metal is coated with a layer of unfilled fluorine-containing rubber (Patent RU 2082469, A 62 B 17/00, 1997).

    [0007] Drawbacks of the known material are its impermeability in respect to moisture vapors released by the human body, a low thermal radiation reflection factor (50-60%), poor adhesion of the metal coating to the layer of fluorine-containing rubber, as a result of which metal particles fall off. In order to strengthen the metal layer, a layer of unfilled fluorine-containing rubber, which chars in open flame for 3-5 seconds, is additionally applied onto the surface of the metal. Wherein, the heat-resistant properties of the material are impaired, the clothes stop fulfilling their functions.

    [0008] A material is known for heat-resistant clothes, which comprises a fabric base and a layer of volumetric metallized material. Fiber glass, which is metallized, applying aluminum in vacuum or by doubling with aluminum foil or with a chrome-plated polymeric film, is used as the volumetric material (Pat RU 2071659, A 41 D 31/00, 1997).

    [0009] Drawbacks of the known material are its insufficiently high reflection factor, unsatisfactory properties in respect to permeability: where the material is doubled with a layer of metal or polymeric film, it acquires air- and vapor-impermeability, including that in respect to moisture vapors released by the human body; where the metal is applied by vacuum deposition onto glass fiber, it becomes moisture-permeable, including in respect to water that is used to extinguish a fire.

    [0010] The material that is the most similar analog to the proposed material is the heat-resistant material comprising a layer of fibrous material, an outer layer of moisture-resistant material with a metallized layer coated with a protective fabric "nomex" of aramide applied thereon, and an inner vapor resistant layer (Patent U.S.A. No. 4502153, 2/81, A 41 D 11/00, 1985).

    [0011] Drawbacks of the known material are the absence therein of vapor- and air-permeability, which does not make it possible to remove the excess moisture from the surface of the body, the low heat reflection factor, which does not make it possible to withstand the power of a heat flow of more than 10 kW/m2 for a lengthy period, and the multilayer construction.

    Summary of the Invention



    [0012] The technical result which is achieved when the invention is carried out is enhancement of the comfort of protective clothes made of the proposed material, which is due to the creation of conditions ensuring the removal of vapors of surplus moisture of the body directly through the heat-resistant material, enhancement of the fire resistant properties, which is due to an increase of the resistance to the action of open fire, preservation of the strength of the material within the period of heat action, an increase of the service life of the clothes, and also simplification of the structure of the material for sewing the clothes, enhancement of its operating properties and effectiveness of the protective action.

    [0013] This result is achieved in that a heat-resistant fireproof material comprising a heat-resistant fiber substrate and a layer of moisture-resistant material with a metal coating layer applied thereon, according to the invention, the layer of moisture-resistant material is made of two layers, one of which comprises a sterically linked polymer having a liquid diffusion coefficient equal or less than 10-9 cm2/sec, the other--a hermetic layer--is made of a rubber-based elastomeric material. In accordance with a variant of the invention, the heat-resistant material comprises a porous material selected from the group of polyolefins, fluorine-, chlorine- or silicon-containing polymers with a pore size of 0.01-1.0 µm as the layer of moisture-resistant material, and aluminum, copper, titanium nitride with a layer thickness of 0.05-0.25 µm as the metal coating layer.

    [0014] The selection of the composition of the layer of moisture-resistant material, made of a sterically linked polymer, on which the metal coating is deposited, is related to the strength characteristics of the heat-resistant/fireproof material. Where the liquid diffusion coefficient of the layer is increased to more than 10-9 cm2/sec (10-8-10-6 cm2/sec), the heat reflection coefficient of the metal coating and the strength of its engagement with the hermetic layer are reduced. The polymer with the sterically linked structure has high resistance to bending as a result of the presence of crosslinkage, which ensures preservation of the original shape and size of the layer thereby formed during the action of heat. Furthermore, the sterically linked polymer has increased resistance to open fire.

    [0015] Chlorosulfonated polyethylene, polytetrafluoroethylene-vinylidene fluoride copolymer, isobutylene-isoprene copolymer, polysulfide polymers (thiocols) and others may be used as the cross-linked polymer.

    [0016] Fluorine-containing, nitrile, polychloroprenene, natural or synthetic polyisoprene, acrylate, polyurethane, epichlorohydrin, silicon and other rubbers may be used as rubbers from which the hermetic layer of the moisture-resistant material, serving to join the fiber substrate and the layer of sterically linked polymer, is made.

    [0017] The heat-resistant fiber substrate may be made from glass fiber, polyaramide, polyimide and other heat-resistant materials.

    [0018] Aluminum, nickel, copper, titanium nitride, steel and others are used as the metal coating layer.

    [0019] The thickness of the metal coating layer for material in which the moisture-resistant layer is made of two layers is 0.15-0.25 µm.

    [0020] In accordance with a variant of the invention, the heat-resistant fireproof material containing a porous material with a pore size of 0.01-1.0 µm is impermeable for water in a liquid aggregate state.

    [0021] Where there are pores having a size greater than 1.0 µm in the layer of moisture-resistant material, the permeability of the material sharply increases in respect to water, where the pores are less than 0.01 µm in size, it becomes virtually vapor-air-impermeable.

    [0022] The heat-resistant fireproof material according to a variant of the invention, containing aluminum, copper, titanium nitride with a metal layer thickness of 0.05-0.25 µm as the metal coating layer, has a high thermal reflection coefficient. An increase of the thickness of the metal layer above 0.25 µm reduces the vapor-air permeability of the material, while a reduction of the thickness to less than 0.05 µm reduces the thermal reflection coefficient.

    [0023] The invention is illustrated by the following examples:

    Example 1



    [0024] A heat-resistant fireproof material is produced by applying a hermetic layer of elastomeric material on the base of filled fluorine-containing rubber onto a cloth layer of glass fabric. A layer on the base of chlorosulfonated polyethylene having a thickness of 0.05 mm and a liquid diffusion coefficient equal to 10-10 cm2/sec is applied onto the prepared cloth layer substrate, and a layer of metallic aluminum is applied onto this polyethylene layer by vacuum deposition.

    [0025] The prepared material has a reflection coefficient of 93%, is stable against the action of open flame (temperature exceeding 1000°C) for 1.5 minutes.

    Example 2



    [0026] A heat-resistant fireproof material is prepared by applying a hermetic layer, made of an elastomeric material on the base of nitrile rubber, onto a fiber layer of polyaramide cloth. A layer on the base of a copolymer - polytetetrafluoroethylene, having a thickness of 3 mm and a liquid diffusion coefficient equal to 10-9 cm2/sec, onto which metallic nickel is further deposited, is applied onto the nitrile rubber substrate. The coefficient of reflection of the prepared material is 96%, resistance against the action of open flame is 1 minute.

    Example 3



    [0027] A heat-resistant fireproof material is prepared by applying a polymeric layer on the base of fluorine-containing polymer having a pore size of 0.2 µm onto glass fiber. Then a layer of aluminum is applied onto the prepared substrate by vacuum deposition to a layer thickness of 0.1 µm.

    [0028] The prepared material is characterized by a coefficient of thermal reflection equal to 90%. Resistance against the action of open flame - 30 sec. The material maintains water impermeability to a water column pressure of 0.3 MPa. Air permeability of the material reaches 150m3/m2.h.MPa.

    Example 4



    [0029] A heat-resistant fireproof material is prepared by applying a layer on the base of a fluorine-containing polymer, having a pore size of 0.01 µm onto a fabric on the base of polyaramide fibers. Further a layer of aluminum is applied to a layer thickness of 0.2 µm onto the first layer by magnetron deposition. The coefficient of heat reflection of the material is 97%. Resistance to the action of open flame is more than 30 sec. The air permeability of the material is 40 m3/m2.h.MPa. The material maintains water impermeability to a water column pressure of 0.6 MPa.

    Example 5



    [0030] A heat-resistant fireproof material is prepared by applying a layer on the base of a silicon-containing polymer to form a porous layer on a fabric on the base of polyamide fibers with a pore size of 1.0 µm, and subsequently applying thereon a copper layer to a layer thickness of 0.25 µm by vacuum deposition. The coefficient of heat reflection of the material is 96%. Resistance to the action of open fire is 25 sec. Air permeability is 120 m3/m2.h.MPa. Water impermeability is maintained to a water jet pressure corresponding to a value of 0.06 MPa.

    Example 6



    [0031] A heat-resistant fireproof material is prepared by applying chlorosulfopolyethylene onto glass fiber to form a layer with a pore size of 0.05 µm with subsequent vacuum deposition thereon of an aluminum layer having a thickness of 0.15 µm. The coefficient of heat reflection of the prepared material is 92%. Resistance to the action of open flame is 25 sec. Air permeability is 60 m3/m2.h.MPa. Water impermeability of the material is maintained to 0.5 MPa.

    Example 7



    [0032] A heat-resistant fireproof material is prepared by applying a layer on the base of chlorosulfopolyethylene, having a pore size of 0.01 µm, onto glass fiber and subsequently applying thereon a layer of titanium nitride, having a thickness of 0.05 µm, by magnetron deposition. The coefficient of heat reflection of the prepared material is 80%. Resistance to the action of open flame is 20 sec. Air permeability is 50 m3/m2.h.MPa. Water impermeability is maintained to water column pressure of 0.5 MPa.

    Example 8



    [0033] A heat-resistant fireproof material is prepared by applying a layer of chlorosulfopolyethylene onto glass fiber to form a porous layer with a pore size of 0.75 µm. Subsequently, a copper layer is applied thereon by vacuum deposition to a layer thickness of 0.1 µm. The coefficient of heat reflection of the prepared material is 85%. Resistance to the action of open flame is 20 sec. Air permeability is equal to 170 m3/m2.h.MPa. Water impermeability is maintained to 0.2 MPa.

    Industrial Applicability



    [0034] Use of the present material for the making of protective clothing for firemen ensures the maintenance of a temperature which does not exceed 24-26°C (with a permissible norm of 50°C) in the under-the-clothing space when there are heat flows with a power of 40 KW/m2 present.

    [0035] Clothes made of the proposed material are elastic and comfortable during multiple use due to the lengthy maintenance of heat- and fire-resistant properties.

    [0036] Thus, as a result of the use of the proposed structure of the material as compared with the material taken as the prototype, the number of layers therein and its weight are reduced, the length of time a person can be in clothes sewed from the proposed material, when working in a zone of high temperatures and open fire, is increased by 2-3 times, the ergonomic parameters of the protective clothes are improved.


    Claims

    1. A heat-resistant fireproof material for making protective clothes comprising a heat-resistant fiber substrate and a layer of moisture-resistant material with a metal coating layer applied thereon by vacuum deposition in a thickness of 0.15-0.25 µm whereby the layer of moisture-resistant material is made of two layers, one of which comprises a sterically linked polymer having a liquid difussion coefficient equal to or less than 10-9 cm2/sec, the other one is made of a rubber-based elastomeric material.
     
    2. A heat resistant fireproof material for making protective clothes comprising a heat-resistant fiber substrate and a layer of moisture-resistant material with a metal coating layer applied thereon by vacuum deposition, whereby it comprises a porous material selected from the group consisting of polyolefins, fluorine-, chlorine- or silicon-containing polymers with a pore size of 0.01-1.0 µm as the layer of moisure-resistant material, and a material selected from the group consisting of aluminium, copper, titanium nitride with a layer thickness of 0.05-0.25 µm as the metal coating layer.
     


    Ansprüche

    1. Hitzebeständiges feuerfestes Material zur Herstellung von Schutzkleidung umfassend ein hitzebeständiges Fasersubstrat und eine Lage aus feuchtigkeitsbeständigem Material mit einer metallischen Beschichtungslage, die durch Aufdampfen im Vakuum in einer Dicke von 0,15 - 0,25 µm darauf angebracht ist, wobei die Lage aus feuchtigkeitsbeständigem Material aus zwei Lagen zusammengesetzt ist, von denen eine ein sterisch verbundenes Polymer mit einem Flüssigkeitsdiffussionskoeffizienten gleich oder kleiner als 10-9 cm2/sec enthält und die andere aus kautschukbasierendem elastomeren Material hergestellt ist.
     
    2. Hitzebeständiges feuerfestes Material zur Herstellung von Schutzkleidung umfassend ein hitzebeständiges Fasersubstrat und eine Lage aus feuchtigkeitsbeständigem Material mit einer metallischen Beschichtungslage, die durch Aufdampfen im Vakuum darauf angebracht ist, wobei es als die Lage aus feuchtigkeitsbeständigem Material ein poröses Material umfasst, das ausgewählt ist aus der Gruppe bestehend aus Polyolefinen, Fluor-, Chlor- oder Silikon-haltigen Polymeren mit einer Porengröße von 0,01- 1,0 µm, und als metallische Beschichtungslage ein Material umfasst, das ausgewählt ist aus der Gruppe bestehend aus Aluminium, Kupfer, Titannitrid mit einer Schichtdicke von 0,05 - 0,25 µm.
     


    Revendications

    1. Matériau ignifuge résistant à la chaleur pour la fabrication de vêtements protecteurs comprenant un substrat de fibres résistant à la chaleur et une couche de matériau résistant à l'humidité avec une couche de revêtement métallique appliquée sur celle-ci par un dépôt sous vide en une épaisseur de 0,15-0,25 µm, en conséquence de quoi la couche de matériau résistant à l'humidité est composée de deux couches, dont l'une comprend un polymère stériquement lié présentant un coefficient de diffusion de liquide inférieur ou égal à 10-9 cm2/sec, l'autre étant faite d'un matériau élastomère à base de caoutchouc.
     
    2. Matériau ignifuge résistant à la chaleur pour la fabrication de vêtements protecteurs comprenant un substrat de fibres résistant à la chaleur et une couche de matériau résistant à l'humidité avec une couche de revêtement métallique appliquée sur celle-ci par un dépôt sous vide, en conséquence de quoi il comprend un matériau poreux choisi dans le groupe constitué de polyoléfines, de polymères contenant du fluor, du chlore ou du silicium avec une taille de pores de 0,01-1,0 µm en tant que matériau résistant à l'humidité, et un matériau choisi dans le groupe constitué d'aluminium, de cuivre, de nitrure de titane avec une épaisseur de couche de 0,05-0,25 µm en tant que couche de revêtement métallique.