EP2411341A1 - Fire retardant comprising glass frit in combination with an additive - Google Patents

Fire retardant comprising glass frit in combination with an additive

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Publication number
EP2411341A1
EP2411341A1 EP10710413A EP10710413A EP2411341A1 EP 2411341 A1 EP2411341 A1 EP 2411341A1 EP 10710413 A EP10710413 A EP 10710413A EP 10710413 A EP10710413 A EP 10710413A EP 2411341 A1 EP2411341 A1 EP 2411341A1
Authority
EP
European Patent Office
Prior art keywords
weight
fire retardant
frit
retardant composition
composition according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP10710413A
Other languages
German (de)
French (fr)
Inventor
Desmond Gerard Eadon
Alan John Newman
Michael John Sinclair
Howard David Winbow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johnson Matthey PLC
Original Assignee
Johnson Matthey PLC
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 Johnson Matthey PLC filed Critical Johnson Matthey PLC
Publication of EP2411341A1 publication Critical patent/EP2411341A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2209/00—Compositions specially applicable for the manufacture of vitreous glazes

Definitions

  • the present invention concerns improvements in inorganic additives suitable for use as fire retardant materials, more especially those inorganic materials known as frits.
  • inorganic materials such as aluminium trihydroxide (ATH), magnesium dihydroxide (MDH), stannates, zinc borate, as well as naturally-occurring minerals including mica and huntite/hydromagnesite systems
  • organic materials such as organic polymers, as fire retardants.
  • fire retardant technology has developed a number of different approaches, including using barrier-forming materials, there remains a need for improved fire retardant additives for solid or liquid compositions.
  • the present invention provides a fire retardant composition
  • a fire retardant composition comprising at least one frit in combination with at least one additive, wherein the frit and the additive are selected such that they undergo one or more reactions under fire conditions to form a structured composition which reduces smoke and toxic gas emissions.
  • structured composition we mean a self- supporting composition which has a degree of mechanical strength.
  • Frits are solid amorphous mixtures of metal oxides and may have melting points from about 250° C to about 1200° C.
  • the frit component of the present invention softens on heating and then melts/flows. This type of behaviour forms a structured composition when it reacts with the additive on combustion.
  • the structured composition has an improved char strength and acts as a barrier layer.
  • the frit preferably forms a froth under fire conditions.
  • the frit can froth and react with the additive to form a structured composition which is voluminous in nature but has good char strength.
  • the char volume is greater than a frit which does not froth.
  • the increased volume advantageously acts as a filter medium further reducing smoke particulates and toxic gas emissions.
  • the frothing properties of the frit are a function of both the frit composition and the processing technique employed to grind the frit to the desired particle size distribution.
  • the frothing may occur because water is physisorbed or chemisorbed onto the frit during the grinding process. This water remains bound after drying at normal temperatures circa 15O 0 C. It is released, however, when heated to higher temperatures, e.g. greater than 300 0 C, to form the frothy glass.
  • the degree of frothing produced will depend on the nature and amount of bound water.
  • the frothing may also be due to the frit dissolving slightly during the grinding process.
  • salts are deposited onto the surface of the frit particles. These salts may then react with the frit during the combustion process. In general, a high alkali metal content will result in higher frit solubility.
  • the frothing may also be due to mechanical stress formed in the frit particle during milling. These are then relieved on heating.
  • Frits according to the invention desirably include significant amounts of silica, as well as boric oxide.
  • the frit also comprises alumina, calcium oxide, sodium oxide, lithium oxide and zirconium oxide.
  • the frit may therefore comprise 15-55% silica, 20-40% boric oxide, 2-15% alumina, calcium oxide in an amount from 0 to 20%, 5-15% sodium oxide, 1-10% lithium oxide, 1-5% zirconium oxide, magnesium oxide in an amount from 0 to 1%, 0.1 to 5% potassium oxide, and optionally other components which do not significantly affect the desired structure-forming properties.
  • the skilled glass chemist may replace one or more components with other components. For example, the skilled glass chemist may formulate frits comprising lead and/or cadium.
  • the skilled glass chemist may also formulate frits comprising phosphate. If desired, the skilled glass chemist may formulate a frit which is RoHS (Restriction of Hazardous Substances) compliant. All percentages are by weight, and it will be understood that the components chosen will together add to 100%.
  • RoHS Restriction of Hazardous Substances
  • the silica is present in an amount from 15 to 49 %, preferably 15 to 45%. In another embodiment, the silica is present in an amount from 51 to 55%.
  • the sodium oxide is present in an amount from 5.5 to 15%. In another embodiment, the sodium oxide is present in an amount from 6 to 13%.
  • the lithium oxide is present in an amount from 2.5 to 10%.
  • the frit component comprises:
  • the frit component comprises: Al 2 O 3 9.3 % by weight B 2 O 3 26.2 % by weight
  • the frit component comprises:
  • the frit is in substantially spherical or substantially psuedospherical form. In another embodiment, the frit is in substantially platelet form.
  • the frit may be prepared for example, by melting the desired components together until homogeneous, then fritting by pouring the glass melt into water to form glass granules.
  • the glass granules are then processed to produce a glass powder of the appropriate dimensions to be incorporated into a polymer system. This processing may be a milling stage to produce spherical / pseudospherical particulates.
  • the frit may also be processed by the spinning cup method, the blown film method or by quenching the molten glass onto a cooled rotating disk to form platelets.
  • Platelet morphology may be advantageous to coherent film formation with orientated platelets giving better surface coverage.
  • the aspect ratio of the platelets can be optimised for different applications (such as opacity), as well as different organic materials.
  • the quenched frit may be ground using, for example, a ball mill, bead mill or high- energy vibro mill.
  • the frit may also be ground in a range of solvents, for example, water, aliphatic hydrocarbons and/or aromatic hydrocarbons. Examples of suitable solvents are white spirits and/or xylene.
  • the quenched frit may also be dried and optionally ground by air jet milling.
  • the mean particle size and the particle size distribution can also be controlled by the comminution technique selected. For example, it is known that bead milling produces a smaller mean particle size than ball milling. In an alternative example, it is also known that both bead milling and air jet milling produce narrower particle size distributions than ball milling.
  • platelet size and aspect ratio can be controlled by varying the processing conditions.
  • the formation of the structured composition is accompanied by one or more exothermic reactions. It appears especially beneficial if the exothermic reaction takes place at about 700° C or above.
  • the additive is in substantially platelet form.
  • the additive preferably comprises at least one of aluminium trihydroxide, magnesium dihydroxide, magnesium carbonate, huntite, hydromagnesite, a "C” glass or an "E” glass.
  • the additive comprises aluminium trihydroxide. In another embodiment, the additive comprises huntite and/or hydromagnesite. In yet another embodiment, the additive comprises a "C" glass and/or an "E” glass (such as those available from NGF Europe under the registered trademark Microglas ® ).
  • the structured composition is substantially porous.
  • the structured composition is at least partially crystalline. It appears even more desirable that the crystallinity increases with increasing temperature.
  • the structured composition comprises Fosterite.
  • the Fosterite forms a major part of the structured composition.
  • Diopside forms a minor part of the structured composition.
  • the toxic gas emissions preferably comprise carbon monoxide.
  • the fire retardant composition of the present invention may further comprise at least one stannate, hydroxystannate or borate.
  • the stannate, hydroxystannate or borate can be used in combination with the mineral fire retardant additive and frit component to adjust the char strength.
  • the materials act as fluxing agents and form glass-like structures at low frit to additive ratios.
  • the borate is calcium borate, which has been found to have a beneficial effect on smoke suppression.
  • the present invention provides a method for enhancing the fire resistance of a material or reducing the surface spread of flame of a material, comprising incorporating within the material, or coating the material with, a fire retardant composition as described above.
  • the material may comprise a solid such as a solid polymeric material.
  • the solid polymeric material is a thermoplast or thermoset.
  • thermoplastic and thermoset polymeric materials are acrylonitrile butadiene styrene (ABS) and other specialist styrenics, aramids PI aromatic polyamide, cellulosics (CA, CAB, CAP, CN), ethylene vinyl acetate (EVA), expanded polypropylene (EPP), fluoroplastics (PTFE and FEP), nylons (polyamides), polyarylether-etherketone (PEEK), polybutene-1 (PB-I), polycarbonate, polyacetals (POM), polyesters (PETP, PBT, PET), polyethyelene (HDPE, LDPE, LLDPE), polypropylene, polyphenylene oxide and sulphide (PPO, PPS), polymethylpentene, polystyrene (GPPS, HIPS), polyvinylchloride (AB
  • the material may comprise at least one brominated flame retardant system, e.g. polybrominated biphenols, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclodecane, tri-o- cresyl phosphate, tris(2,3-dibromopropyl) phosphate (TRIS), bis(2,3-dibromopropyl) phosphate or the like.
  • a brominated flame retardant system e.g. polybrominated biphenols, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclodecane, tri-o- cresyl phosphate, tris(2,3-dibromopropyl) phosphate (TRIS), bis(2,3-dibromopropyl
  • the structured composition of the present invention is beneficial in reducing the emission of halogen-containing toxic gas emissions (for example, HCl or HBr gases).
  • the material may comprise at least one phosphorous compound e.g. tetrakis(hydroxymethyl) phosphonium salts, ammonium polyphosphate compounds, organophosphates, halogenated phosphates, red phosphorous or tris(l-aziridinyl)-phosphine oxide (TEPA).
  • phosphorous compound e.g. tetrakis(hydroxymethyl) phosphonium salts, ammonium polyphosphate compounds, organophosphates, halogenated phosphates, red phosphorous or tris(l-aziridinyl)-phosphine oxide (TEPA).
  • the material may comprise melamine or a derivative thereof.
  • Melamine derivatives include, for example, salts with organic or inorganic acids such as boric acid, cyanuric acid, phosphoric acid or pyro/poly-phosphoric acid, and melamine homologues.
  • the material may comprise a solid material which uses a polymeric binder, such as glass- fibre-reinforced plastics, or composites such as wood chip composites, or liquids having a high organic content such as many paints.
  • a polymeric binder such as glass- fibre-reinforced plastics, or composites such as wood chip composites, or liquids having a high organic content such as many paints.
  • the material may comprise silicone.
  • the material comprising silicone may be foamed.
  • Suitable loadings of the additive and the frit in the material are from about 10 to about 90 parts per hundred material, preferably from about 20 to about 70 parts per hundred and more preferably from about 20 to about 60 parts per hundred material.
  • the material may comprise other components which are intended to improve resistance to fire, to add strength, as well as fillers, pigments or dyes.
  • the effectiveness of the invention is such that additive and frit component combinations may be devised which can be used in reduced quantities compared to more traditional mineral fire retardants, which improves processing options.
  • Example 2 properties of frit, mineral additive and mixture
  • STA analysis was carried out up to 1000 0 C at a rate of 10° C per minute on a commercially-available fire retardant, based upon (a) a naturally-occurring mineral mixture of huntite and hydromagnesite, (b) Frit 1 and (c) an admixture of huntite/hydromagnesite and Frit 1.
  • the huntite/hydromagnesite product exhibited four distinct endotherms, corresponding to releases of water vapour and carbon dioxide. No exotherms were detected. In the case of Frit 1, there were no significant endothermic or exothermic changes, but beginning at about 700° C, there was a noticeable increase in sample weight.
  • XRD analysis was carried out, and identified that a major phase of Fosterite (crystalline magnesium silicate) and a minor proportion of Diopside (CaMgSi 2 O 6 ) formed at about 730-735° C.
  • Fosterite crystalline magnesium silicate
  • CaMgSi 2 O 6 Diopside
  • the Example was carried out in accordance with IMO Resolution MSC 61(67); Annex 1, Part 2.
  • the formulation containing aluminium trihydroxide (ATH) and Frit 2 passes the smoke, CO and Cl tests and has good char strength, unlike samples 1 or 2.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a fire retardant composition comprising at least one frit in combination with at least one additive, wherein the frit and the additive are selected such that they undergo one or more reactions under fire conditions to form a structured composition which reduces smoke and toxic gas emissions. A method for enhancing the fire resistance of a material or reducing the surface spread of flame of a material is also described.

Description

FIRE RETARDANT COMPRISING GLASS FRIT IN COMBINATION WITH AN
ADDITIVE
The present invention concerns improvements in inorganic additives suitable for use as fire retardant materials, more especially those inorganic materials known as frits.
It is known to add inorganic materials, such as aluminium trihydroxide (ATH), magnesium dihydroxide (MDH), stannates, zinc borate, as well as naturally-occurring minerals including mica and huntite/hydromagnesite systems, to organic materials such as organic polymers, as fire retardants. Although fire retardant technology has developed a number of different approaches, including using barrier-forming materials, there remains a need for improved fire retardant additives for solid or liquid compositions.
It has also been described in GB 2 203 157 and GB 2 234 754 that mixtures of two or more frits can be useful additives for organic materials, suitably together with traditional fire retardants such as antimony oxide or hydrated magnesium calcium carbonate.
In one aspect, the present invention provides a fire retardant composition comprising at least one frit in combination with at least one additive, wherein the frit and the additive are selected such that they undergo one or more reactions under fire conditions to form a structured composition which reduces smoke and toxic gas emissions.
It is believed that the at least one frit and the at least one additive synergistically react to form the structured composition. By "structured composition", we mean a self- supporting composition which has a degree of mechanical strength.
Frits are solid amorphous mixtures of metal oxides and may have melting points from about 250° C to about 1200° C.
The frit component of the present invention softens on heating and then melts/flows. This type of behaviour forms a structured composition when it reacts with the additive on combustion. The structured composition has an improved char strength and acts as a barrier layer.
The frit preferably forms a froth under fire conditions.
In the fire retardant composition, the frit can froth and react with the additive to form a structured composition which is voluminous in nature but has good char strength. The char volume is greater than a frit which does not froth. The increased volume advantageously acts as a filter medium further reducing smoke particulates and toxic gas emissions.
Without wishing to be bound by theory, it is believed that the frothing properties of the frit are a function of both the frit composition and the processing technique employed to grind the frit to the desired particle size distribution.
In respect of the processing technique, the frothing may occur because water is physisorbed or chemisorbed onto the frit during the grinding process. This water remains bound after drying at normal temperatures circa 15O0C. It is released, however, when heated to higher temperatures, e.g. greater than 3000C, to form the frothy glass. The degree of frothing produced will depend on the nature and amount of bound water.
The frothing may also be due to the frit dissolving slightly during the grinding process. On drying the frit, salts are deposited onto the surface of the frit particles. These salts may then react with the frit during the combustion process. In general, a high alkali metal content will result in higher frit solubility.
The frothing may also be due to mechanical stress formed in the frit particle during milling. These are then relieved on heating.
Frits according to the invention desirably include significant amounts of silica, as well as boric oxide. Desirably, the frit also comprises alumina, calcium oxide, sodium oxide, lithium oxide and zirconium oxide. The frit may therefore comprise 15-55% silica, 20-40% boric oxide, 2-15% alumina, calcium oxide in an amount from 0 to 20%, 5-15% sodium oxide, 1-10% lithium oxide, 1-5% zirconium oxide, magnesium oxide in an amount from 0 to 1%, 0.1 to 5% potassium oxide, and optionally other components which do not significantly affect the desired structure-forming properties. The skilled glass chemist may replace one or more components with other components. For example, the skilled glass chemist may formulate frits comprising lead and/or cadium. Alternatively or in addition, the skilled glass chemist may also formulate frits comprising phosphate. If desired, the skilled glass chemist may formulate a frit which is RoHS (Restriction of Hazardous Substances) compliant. All percentages are by weight, and it will be understood that the components chosen will together add to 100%.
In one embodiment, the silica is present in an amount from 15 to 49 %, preferably 15 to 45%. In another embodiment, the silica is present in an amount from 51 to 55%.
In one embodiment, the sodium oxide is present in an amount from 5.5 to 15%. In another embodiment, the sodium oxide is present in an amount from 6 to 13%.
In one embodiment, the lithium oxide is present in an amount from 2.5 to 10%.
In one embodiment, the frit component comprises:
Al2O3 3.8 % by weight
B2O3 26.1 % by weight
BaO 0 % by weight
CaO 0.1 % by weight K2O 0.3 % by weight
Li2O 2.5 % by weight
MgO 0.2 % by weight
Na2O 11.6 % by weight
SiO2 52.7 % by weight ZnO 0 % by weight and
ZrO2 2.7 % by weight.
In another embodiment, the frit component comprises: Al2O3 9.3 % by weight B2O3 26.2 % by weight
BaO 0 % by weight
CaO 16.8 % by weight
K2O 2.5 % by weight
Li2O 5.6 % by weight
MgO 0.1 % by weight
Na2O 8.0 % by weight
SiO2 29.0 % by weight
ZnO 0 % by weight and
ZrO2 2.5 % by weight.
In yet another embodiment, the frit component comprises:
Al2O3 9.0 % by weight
B2O3 35.0 % by weight
BaO O % by weight
CaO 17.0 % by weight
K2O 2.5 % by weight
Li2O 5.5 % by weight
MgO O % by weight
Na2O 8.0 % by weight
SiO2 20.5 % by weight
ZnO O % by weight and
ZrO2 2.5 % by weight.
In one embodiment, the frit is in substantially spherical or substantially psuedospherical form. In another embodiment, the frit is in substantially platelet form.
The frit may be prepared for example, by melting the desired components together until homogeneous, then fritting by pouring the glass melt into water to form glass granules. The glass granules are then processed to produce a glass powder of the appropriate dimensions to be incorporated into a polymer system. This processing may be a milling stage to produce spherical / pseudospherical particulates. Alternatively, the frit may also be processed by the spinning cup method, the blown film method or by quenching the molten glass onto a cooled rotating disk to form platelets. Platelet morphology may be advantageous to coherent film formation with orientated platelets giving better surface coverage. The aspect ratio of the platelets can be optimised for different applications (such as opacity), as well as different organic materials.
The quenched frit may be ground using, for example, a ball mill, bead mill or high- energy vibro mill. The frit may also be ground in a range of solvents, for example, water, aliphatic hydrocarbons and/or aromatic hydrocarbons. Examples of suitable solvents are white spirits and/or xylene.
The quenched frit may also be dried and optionally ground by air jet milling.
The mean particle size and the particle size distribution can also be controlled by the comminution technique selected. For example, it is known that bead milling produces a smaller mean particle size than ball milling. In an alternative example, it is also known that both bead milling and air jet milling produce narrower particle size distributions than ball milling.
Similarly, platelet size and aspect ratio can be controlled by varying the processing conditions.
Initial tests have clarified that a given frit may not form an adequate structure with the mineral additive, whereas an alternative frit may do so. Thus, there appears to be one or more specific reactions taking place between the additive and the frit component that is dependent upon the chemical constitution of the additive and the frit. Contrary to the teaching of the two GB patent publications mentioned above, there appears to be no need to assess physical properties such as melting point, but rather the need is to assess the ability of the frit to form a structure with the additive.
It appears desirable that the formation of the structured composition is accompanied by one or more exothermic reactions. It appears especially beneficial if the exothermic reaction takes place at about 700° C or above. Preferably, the additive is in substantially platelet form.
The additive preferably comprises at least one of aluminium trihydroxide, magnesium dihydroxide, magnesium carbonate, huntite, hydromagnesite, a "C" glass or an "E" glass.
In one embodiment, the additive comprises aluminium trihydroxide. In another embodiment, the additive comprises huntite and/or hydromagnesite. In yet another embodiment, the additive comprises a "C" glass and/or an "E" glass (such as those available from NGF Europe under the registered trademark Microglas®).
Initial trials indicate that the quantity of frit relative to mineral additive is suitably from about 10:90 to about 90:10 and more suitably about 20:80 to about 40:60 by weight. It has also been found that the strength of the char can be adjusted by varying the frit to additive ratio.
Preferably, the structured composition is substantially porous.
It appears desirable that the structured composition is at least partially crystalline. It appears even more desirable that the crystallinity increases with increasing temperature.
Preferably, the structured composition comprises Fosterite.
More preferably, the Fosterite forms a major part of the structured composition.
Even more preferably, Diopside forms a minor part of the structured composition.
The toxic gas emissions preferably comprise carbon monoxide.
The fire retardant composition of the present invention may further comprise at least one stannate, hydroxystannate or borate. The stannate, hydroxystannate or borate can be used in combination with the mineral fire retardant additive and frit component to adjust the char strength. The materials act as fluxing agents and form glass-like structures at low frit to additive ratios. Preferably, the borate is calcium borate, which has been found to have a beneficial effect on smoke suppression.
In another aspect, the present invention provides a method for enhancing the fire resistance of a material or reducing the surface spread of flame of a material, comprising incorporating within the material, or coating the material with, a fire retardant composition as described above.
The material may comprise a solid such as a solid polymeric material. Preferably, the solid polymeric material is a thermoplast or thermoset. Examples of thermoplastic and thermoset polymeric materials are acrylonitrile butadiene styrene (ABS) and other specialist styrenics, aramids PI aromatic polyamide, cellulosics (CA, CAB, CAP, CN), ethylene vinyl acetate (EVA), expanded polypropylene (EPP), fluoroplastics (PTFE and FEP), nylons (polyamides), polyarylether-etherketone (PEEK), polybutene-1 (PB-I), polycarbonate, polyacetals (POM), polyesters (PETP, PBT, PET), polyethyelene (HDPE, LDPE, LLDPE), polypropylene, polyphenylene oxide and sulphide (PPO, PPS), polymethylpentene, polystyrene (GPPS, HIPS), polyvinylchloride (plasticised and rigid), styrene acrylonitrile (SAN) and acrylonitrile-styrene acrylate (ASA), thermoplastic elastomers (TPE, TPR), allylics (DAP, DAIP, ADC), alkyds (AMC), epoxies (EP), furan, melamines/ure (aminos, MF, UF), phenolics (PF), polyurethane cast elastomers (EP), polyurethane foams, unsaturated polyester (EP), vinyl esters. More preferably, the solid polymeric material is polyvinylchloride.
In another embodiment, the material may comprise at least one brominated flame retardant system, e.g. polybrominated biphenols, pentabromodiphenyl ether, octabromodiphenyl ether, decabromodiphenyl ether, hexabromocyclodecane, tri-o- cresyl phosphate, tris(2,3-dibromopropyl) phosphate (TRIS), bis(2,3-dibromopropyl) phosphate or the like.
When the material comprises a halogen (such as polyvinylchloride or a brominated flame retardant system), the structured composition of the present invention is beneficial in reducing the emission of halogen-containing toxic gas emissions (for example, HCl or HBr gases).
In yet another embodiment, the material may comprise at least one phosphorous compound e.g. tetrakis(hydroxymethyl) phosphonium salts, ammonium polyphosphate compounds, organophosphates, halogenated phosphates, red phosphorous or tris(l-aziridinyl)-phosphine oxide (TEPA).
In another embodiment, the material may comprise melamine or a derivative thereof. Melamine derivatives include, for example, salts with organic or inorganic acids such as boric acid, cyanuric acid, phosphoric acid or pyro/poly-phosphoric acid, and melamine homologues.
In another embodiment, the material may comprise a solid material which uses a polymeric binder, such as glass- fibre-reinforced plastics, or composites such as wood chip composites, or liquids having a high organic content such as many paints.
In yet another embodiment, the material may comprise silicone. Suitably, the material comprising silicone may be foamed.
Suitable loadings of the additive and the frit in the material are from about 10 to about 90 parts per hundred material, preferably from about 20 to about 70 parts per hundred and more preferably from about 20 to about 60 parts per hundred material.
In addition to the mineral additive and the frit component, the material may comprise other components which are intended to improve resistance to fire, to add strength, as well as fillers, pigments or dyes. The effectiveness of the invention is such that additive and frit component combinations may be devised which can be used in reduced quantities compared to more traditional mineral fire retardants, which improves processing options. The invention will now be described with reference to the following non-limiting Examples.
Example 1 - Frit Production
Using conventional methods, three different frits were produced:
Frit 1 2 3
Component % by wt
Al2O3 3.8 9.3 9.0
B2O3 26.1 26.2 35.0
BaO O O O
CaO 0.1 16.8 17.0
K2O 0.3 2.5 2.5
Li2O 2.5 5.6 5.5
MgO 0.2 0.1 0
Na2O 11.6 8.0 8.0
SiO2 52.7 29.0 20.5
ZnO O O 0
ZrO2 2.7 2.5 2.5
Total 100 100 100
Example 2 - properties of frit, mineral additive and mixture
STA analysis was carried out up to 10000C at a rate of 10° C per minute on a commercially-available fire retardant, based upon (a) a naturally-occurring mineral mixture of huntite and hydromagnesite, (b) Frit 1 and (c) an admixture of huntite/hydromagnesite and Frit 1.
The huntite/hydromagnesite product exhibited four distinct endotherms, corresponding to releases of water vapour and carbon dioxide. No exotherms were detected. In the case of Frit 1, there were no significant endothermic or exothermic changes, but beginning at about 700° C, there was a noticeable increase in sample weight.
70 parts by weight of the huntite/hydromagnesite product were intimately mixed with 30 parts by weight of Frit 1, and the the STA analysis repeated. The same four endotherms were observed as with the huntite/hydromagnesite product, but at 734° C, an unexpected exotherm was observed. The weight of the sample then became constant.
XRD analysis was carried out, and identified that a major phase of Fosterite (crystalline magnesium silicate) and a minor proportion of Diopside (CaMgSi2O6) formed at about 730-735° C.
Example 3 - fire tests
The Example was carried out in accordance with IMO Resolution MSC 61(67); Annex 1, Part 2.
As can be seen from the table, the formulation containing aluminium trihydroxide (ATH) and Frit 2 (i.e. sample 3) passes the smoke, CO and Cl tests and has good char strength, unlike samples 1 or 2.

Claims

1. A fire retardant composition comprising at least one frit in combination with at least one additive, wherein the frit and the additive are selected such that they undergo one or more reactions under fire conditions to form a structured composition which reduces smoke and toxic gas emissions.
2. A fire retardant composition according to claim 1, wherein the frit forms a froth under fire conditions.
3. A fire retardant composition according to claim 1 or claim 2, wherein the frit comprises 15-55% silica, 20-40% boric oxide, 2-15% alumina, calcium oxide in an amount from 0 to 20%, 5-15% sodium oxide, 1-10% lithium oxide, 1-5% zirconium oxide, magnesium oxide in an amount from 0 to 1%, 0.1 to 5% potassium oxide, and optionally other components which do not significantly affect the desired structure- forming properties, the whole adding up to 100% by weight.
4. A fire retardant composition according to any one of the preceding claims, wherein the frit comprises:
Al2O3 3.8 % by weight
B2O3 26.1 % by weight
BaO 0 % by weight
CaO 0.1 % by weight
K2O 0.3 % by weight
Li2O 2.5 % by weight
MgO 0.2 % by weight
Na2O 11.6 % by weight
SiO2 52.7 % by weight
ZnO 0 % by weight and
ZrO2 2.7 % by weight.
5. A fire retardant composition according to any one of the claims 1 to 3, wherein the frit comprises:
Al2O3 9.3 % by weight B2O3 26.2 % by weight
BaO 0 % by weight
CaO 16.8 % by weight
K2O 2.5 % by weight
Li2O 5.6 % by weight
MgO 0.1 % by weight
Na2O 8.0 % by weight
SiO2 29.0 % by weight
ZnO 0 % by weight and
ZrO2 2.5 % by weight.
6. A fire retardant composition according to any one of claims 1 to 3, wherein the frit comprises:
Al2O3 9.0 % by weight B2O3 35.0 % by weight
BaO O % by weight
CaO 17.0 % by weight
K2O 2.5 % by weight
Li2O 5.5 % by weight MgO O % by weight
Na2O 8.0 % by weight
SiO2 20.5 % by weight
ZnO O % by weight and
ZrO2 2.5 % by weight.
7. A fire retardant composition according to any one of the preceding claims, wherein the frit is in substantially platelet form.
8. A fire retardant composition according any one of claims 1 to 6, wherein the frit is in substantially spherical or substantially psuedospherical form.
9. A fire retardant composition according to any one of the preceding claims, wherein the additive is in substantially platelet form.
10. A fire retardant composition according to any one of the preceding claims, wherein the additive comprises at least one of aluminium trihydroxide, magnesium dihydroxide, magnesium carbonate, huntite, hydromagnesite, a "C" glass or an "E" glass.
11. A fire retardant composition according to any one of the preceding claims, wherein the additive comprises aluminium trihydroxide.
12. A fire retardant composition according to any one of claims 1 to 10, wherein the additive comprises huntite, hydromagnesite or combinations thereof.
13. A fire retardant composition according to any one of claims 1 to 10, wherein the additive comprises a "C" glass, an "E" glass or combinations thereof.
14. A fire retardant composition according to any one of the preceding claims, wherein the proportion of frit to additive is from about 10:90 to about 90:10 by weight.
15. A fire retardant composition according to any one of the preceding claims, wherein the reaction is an exothermic reaction.
16. A fire retardant composition according to claim 15, wherein the exothermic reaction takes place at about 7000C or above.
17. A fire retardant composition according to any one of the preceding claims, wherein the structured composition is substantially porous.
18. A fire retardant composition according to any one of the preceding claims, wherein the structured composition is at least partially crystalline.
19. A fire retardant composition according to any one of the preceding claims, wherein the structured composition comprises Fosterite.
20. A fire retardant composition according to claim 19, wherein the Fosterite forms a major part of the structured composition.
21. A fire retardant composition according to claim 20, wherein Diopside forms a minor part of the structured composition.
22. A fire retardant composition according to any one of the preceding claims, wherein the toxic gas emissions comprise carbon monoxide.
23. A fire retardant composition according to any one of the preceding claims, further comprising at least one stannate, hydroxystannate or borate.
24. A method for enhancing the fire resistance of a material or reducing the surface spread of flame of a material, comprising incorporating within the material, or coating the material with, a fire retardant composition according to any one of claims 1 to 23.
25. A method according to claim 24, wherein the material comprises: (a) a solid polymeric material; (b) at least one brominated flame retardant system;
(c) at least one phosphorus compound;
(d) melamine or a derivative thereof;
(e) a solid material which uses a polymeric binder;
(f) composites; (g) liquids having a high organic content; or
(h) silicone.
26. A method according to claim 25, wherein the solid polymeric material is a thermoplast or a thermoset.
27. A method according to claim 25 or claim 26, wherein the solid polymeric material comprises polyvinylchloride.
28. A method according to any one of claims 24 to 27, wherein the material comprises a halogen and the fire retardant composition reduces toxic gas emissions further comprising a halogen-containing gas.
29. A method according to any one of claims 24 to 28, wherein the loading of additive and frit in the material is from about 10 to about 90 parts per hundred material.
30. A frit component comprising 15-55% silica, 20-40% boric oxide, 2-15% alumina, calcium oxide in an amount from 0 to 20%, 5-15% sodium oxide, 1-10% lithium oxide, 1-5% zirconium oxide, magnesium oxide in an amount from 0 to 1%, 0.1 to 5% potassium oxide, and optionally other components, the whole adding up to 100% by weight.
31. A frit component according to claim 30, which comprises:
Al2O3 3.8 % by weight
B2O3 26.1 % by weight
BaO 0 % by weight
CaO 0.1 % by weight
K2O 0.3 % by weight
Li2O 2.5 % by weight
MgO 0.2 % by weight
Na2O 11.6 % by weight
SiO2 52.7 % by weight
ZnO 0 % by weight and
ZrO2 2.7 % by weight.
32. A frit component according to claim 30, which comprises:
Al2O3 9.3 % by weight B2O3 26.2 % by weight
BaO 0 % by weight
CaO 16.8 % by weight
K2O 2.5 % by weight
Li2O 5.6 % by weight MgO 0.1 % by weight
Na2O 8. 0 % by weight
SiO2 29. 0 % by weight
ZnO 0 % by weight and
ZrO2 2.5 % by weight.
33. A frit component according to claim 30, which comprises:
Al2O3 9.0 % by weight
B2O3 35.0 % by weight
BaO O % by weight
CaO 17.0 % by weight
K2O 2.5 % by weight
Li2O 5.5 % by weight
MgO O % by weight
Na2O 8.0 % by weight
SiO2 20.5 % by weight
ZnO 0 % by weight and
ZrO2 2.5 % by weight.
EP10710413A 2009-03-25 2010-03-17 Fire retardant comprising glass frit in combination with an additive Withdrawn EP2411341A1 (en)

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GB0905130A GB0905130D0 (en) 2009-03-25 2009-03-25 Improvements in inorganic additives
PCT/GB2010/050460 WO2010109218A1 (en) 2009-03-25 2010-03-17 Fire retardant comprising glass frit in combination with an additive

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