GB2234754A

GB2234754A - Fire-retardant additives and their uses

Info

Publication number: GB2234754A
Application number: GB9022308A
Authority: GB
Inventors: Geoffrey Crompton
Original assignee: Individual
Current assignee: Individual
Priority date: 1987-04-11
Filing date: 1990-10-12
Publication date: 1991-02-13
Anticipated expiration: 2008-04-11
Also published as: GB9022308D0; GB2234754B

Description

Title: Fire retardant additives and their uses.

DESCRIPTION This invention concerns additive compositions for use in providing or enhancing fire resistance C materials and compositions and a method of providing or enhancing fire resistance properties for materials and compositions.

If alumina trihydrate is used as an additive to plastics materials, as a firo retardant, several difficulties emerge. Alumina trinydrate produces water, up to 30 of its weight, at temperatures of 200 degrees C. This water turns to steam and blankets burning action. It follows therefore, that alumina trihydrate cannot be used in plastics materials whicn are processed at temperatures above 185 degrees C (to leave a safety margin). Suc plastics materials nclude polypropylene and polyethylene.

Secondly, to be effective, levels of 60 by weight and even 64 by weight of alumina trihydrate have been used in urethane methacrylate and polyesters.

Such high amounts of a filling make the resin very difficult to work.

Thirdly, alumina trhydrate is suppliec in various grades priced according to their micron size.

The cheapest is at 25 micron particle size, the dearest at about 10 micron. The larger particles are in plate form which makes them difficult to disperse in high concentrations, and that can also have an adverse effect on surface finish. The smaller particles are rounded during processing and disperse more easily but are more expensive by a factor of three compared to the larger particles.

Another popular fire refiardant additive Is antimony oxide. - This material contains 3a arsenic and consequently renders any product containing it toxic.

Antimony oxide works by combining with tree halogen but is only partially effective, in that it improves existing ire -etardant properties rather than making materials conform to rigorous testis. Antimony oxide is usally used in amounts of 3% by weight, although higher amounts may be used in some materials.

One obJect of the present invention is to provide an additive composition that can be used tor the purpose of providing or enhancing fire resistance of materials and compositions.

Another obJect of the present invention is to provide a method oi providing or enhancing zaire resistance properties for materials and compositions, According to one aspect of this invention there is provided an additive composition for use in providing or enhancing fire resistance formaterials and compositions comprising two or more frits and optionally ceramic and/or basalt fibres or powder.

According to another aspect o this inventIon there is provided a method of providing or enhancing fire resistance properties for a material or composition comprising adding to said material or composition a composition comprising two or more frits and optionally ceramic and/or basalt fibres or powder.

preferably a combination of frits of different melting points are used in the compositions of the invention to provide continuous flow of molten frit as temperatures increase. A devitrifying frit is a desirable component of the additive of the invention as that tends to solidify after melting to provide strength. The trits under fire conditions wil me progressively to provide a fused protective layer. A preterrec -rit combination comprises a low melting frit e.g. that starts to melt at about 450 degrees C and a high melting or devitrifylng frit that starts to melt at about 700 degrees C. The preferred weight ratio of low melt frit to high melt trit s in the range 1:9 to i:', especIally 3:7. A typical selection of frits may be from those that melt at or about the following temperatures: 450 degrees C, 650 degrees C, 850 degrees c and 1000 degrees C. The frits used are preferably oven dried, water washed and ground prior to inclusion in the compositions of the invention.

The inclusion of ceramic in fibre or powder form can be used to bind the melting frits and also to remain unchanged at temperatures above 1000 degrees C.

Basalt fibre or chopped fibre or powder can also be used n place of or ln addition to the ceramic material.

The compositions of the invention may also comprise one Cr more other fire retardant additives.

or example an Intumescent substance or substances may be Included -n the compositions o the invention, sucn as alumina trihydrate which releases most of its chemically combined water between 200 and 330 degrees C to dampen burning and reduce smoke emission or hydrated magnesium calcIum carbonate which releases its cnemically combined water and carbon dioxide from 230 degrees C upwards. For some purposes hydrated magnesium calcium carbonate may be preferable to alumIna trihydrate because it Is less expensive to obtain in very fInely dIvided form say of the order to 2 to 3 particle size. A preferred composition of frits and intumescent substance or substances comprises from 15-80, especially 20-30, by weight of frits and 85 to 50, especially 80-70, 7 by weight of intumescent substance(s). Another example of fire retardant additives may be antimony oxide usually used in comblnat ton with halogenated hydrocarbon, whereby halogen free radIcals are produced that suppress burning.

The proportion of frits to ceramic or basalt in a preferred embodiment of the invention is about 7:3.

The compositions of the invention may be added to a variety of materials such as polymers, paints and sodium silicate. Suitable polymers include polyesters, phenolic resins, polyurethanes and other thermosetting resIns and thermoplastlcs. If, however, alumina trihydrate is to be included in the additive composition, the composition cannot be used on materials processed at 200 degrees C or more preferably at 185 dgrees C or more.

In a phenolic resin, for example, the proportion of an additlve composition of the invention comprising frits and ceramic or basalt to resin may be from 3:7 to The frits additive with intumescent substance, such as hydrated magnesium calcium carbonate or alumina trihydrate or a mixture thereof, may be added to dough moulding compounds, such as of the phenolic or polyester type to be used with glass reinforcement.

Preferably the ratio of writs to intumescent is about 1 o.

or addition to pheno ic resin frit/intumescent substance mix ratio in the range of from 7:3 to5:5 may be used. the preferred ratio of that mix to phenols resin being in the range of 3:7 to 4:6.

The action of heat on a resin which contains an additive compositIon according to the invention has the following effect. The resin or plastic materials burns and the frit in the first temperature band melts and combines with the char. The second Trips then melts and so on. The substrate and burning material are encapsulated by the molten frits thus starving the fire of oxygen. The ceramic or basalt or both, if present, insulate and stiffen the molten mass to prevent excessive running. They also contribute greatly to stability at high temperatures.

Since the particle size of the frits and ceramic can be controlled they are suitable for use with alumina trihydrate in its course form. The particles will the gaps between the alumina trihydrate plates to g-ve a better inish. The p t ates of alumina trihydrate act as a suspension agent for the frits/ceramic mix.

The water produced in the form of steam nas a beneficial effect on the frits, which are water soluble, aiding in the coating action.

The addition of mixes to sodium silicate has a beneficial effect, in tnat the frits tend to plasticise the sodium silicate under increasing temperature conditions, this counteracts the embrittlement and powdering of the sodium silicate normally encountered in these conditIons. The inclusIon of frits ;n an Intumescent seal or paint formula would constitute an improvement.

It is preferred to use a mix of frits and intumescent substance, such as hydrated magnesium calcium carbonate or alumina trihydrate or a mixture thereof, say in the ratio of 3:7 to 1:1, preferably 4:6, with sodium silicate and by varying the ratio of the frit mix to sodium silicate materials suitable for different uses may be obtained. At a ratio about 1:1 the resultant mixture has a paint consistency at a ratio of aboiut 7:13 the mixture has adhesive properties and at a ratio of about 1:4 the mixture is in a gel form.

The fritz composition of the invention may be used to make sealant say for around fire doors or windows. The preferred sealant will swell when heated and stop any gaps around say doors or windows.

or a sealant paste a frit combination containing intumescent with sodium silicate say In the ratio of 3:7 to 4:6, preferaby 7:13 by weight may be used as a base to whIch is added a char agent, such as mica, ammonlum polyphospha e and an inorganic gelling agent.

The resultant paste is one which will harden in situ.

By using polyvinylacetate in place of the sodium silicate, a resilient sealant may be produced that ili swell and harden when heated.

Another possible use of the aditive composition of She invention is in the production of sheets or boards made by compression o chips of wood wtn a oncer. Thus, the blinder may be a composition comprising phenolic resin or sodium silicate solution containing ceramics such as carborundum, and frits, preferably three frits having different melt temperatures.

A further use of the additive composition of the invention may be as an adhesive. The preferred adhesive will be based on sodium silicate solution containing a catalyst of phenolic resin and the composItion of the invention. Such an adhesive may be used In circumstances where fire resistance is important.

For example, the adhesive may be used for bonding facing sheets, such as of nelamine, to a base material, such as chipboard. Then under fire conditions, the adhesIve can provide a protective shield for the base material even wnen the facing sheet has been burnt of-.

Another particular use is as an adhesIve for attachIng a brake lining to Its carrier. Indeed brake linings may be made rom the same composition, the ceramic material preferably being slag fibre and shot, such as produced as waste from power stations. he brake linings material may comprise additional strengthening components, such as carbon fibre or thermoplastics material e.g. KEVLAR (trade name).

Another example of using frits is in he construction of a laminate comprising an outer skin formed by heat and pressure where a glass cloth has been impregnated with a liquid settable resin, such as phenolic, containing frits of different melt temoeratures together with a binding heat stable, fibre, such as ceramic mullite fibre, and optionally alumina trihydrate. The skins of impregnated cloth are place on ether sle of a ceramic paper, combination basalt, ceramic and glass fibre paper, lass cloth treated v.ih vermiculite or indeed any heat resistance barrier material. When this laminate is pressed under heat and with any number of interleaved sheets the settable resin migrates Into the barrier material to produce a solid sheet.

When flame is applied to the laminate the settao.'e resin turns to protect the substrate, the barrier material providing stability.

The surface of the laminate may be covered with melamine sheet either plain or patterned or real wood veneer when flamne is applied, the frits/ceramic heip to form a char and prevent spread of flame. This moulded laminate, flat or three dimensional, can then be adhered to a substrate, such as a door, using sodium silicate containing the same frits, ceramic .-iore and optionally V alumina trihydrate previously mentioned to make a high heat performance adhesive.

The substrate can be a rigidized sheet o ceramic fibre which is in turn adhered with the adhesIve described, to a heat resistance sound deadening core made from say basalt fibre or rockwool rigidized or non-rigidlzed. The construction may be repeated about the centre line.

For thirty minute rating the pressed laminates adhered and/or mechanically fixed to a basalt or rockwool core is sufficient. For sIxty minute rating the rigidized ceramic board may be introduced, and for extended times the ceramic board can be increased in thickness and a ceramic non-rigid blanket can be used instead of the rockwool/basalt core. For light weight construct Ions a phenolic foam core or a foam made from the adhesive mentioned can be used.

A foamed vermiculite clay can be included in the adhesive to produce a lightweight, highly insulating core. Alternatively a core can be made by using woodchlp as a filler to the adhesive to make a high heat resIstance chipboard core to a door, building panel or partition.

This invention will now be further described by means of the following Examples.

Example 1 A polyester resin containing 20 by weight of alumina trihydrate and 16% by weight of frits and 4% by weight of ceramic powder was found to have enhanced fire resistance.

Example 2 A phenolic resin containing 30J by weight of a mixture of frits (80V by weight) and ceramic powder '20 by weight) passed 3S 476 part 8 90 minutes ir resistance test.

Example 3 A mix containing antimony oxide 3% by weight, one rit at a low temperature melt band at lOa by weight, one frit at a high temperature melt band (of approximately 1100 degrees C) at 60 by weight and ceramic at 27% by weight made up a casting or injection material which was suitable for use wit a phenolic or sodium silicate binder as well as other materials including thermosets and thermoplastics.

Example 4 A mix containing antimony oxide 3% by weight, one frit at a low tzmperature melt band at 7% by weight, one frit at a high temperature melt band (of approximately 1100 degrees C) at 4O by weight and alumina trihydrate at 43% by weight made a mix suitable cr polyesters and other materias Including thermosetting resins whose processing is not done above 185 degrees C.

Example 5 A basic powder mix was produced from 40% by weight of a combination of a low melting frit (450 degrees C) and a high melting (devitrifying) frit (700 degrees C) in the weight ratio of 3:7 and 60% of hydrated magnesiums calcium carbonate.

An adhesive composition was produced by adding 35% by weight of the powder mix to 65% by weight of sodium silicate.

Example 6 A oaint-like composition was produced by adding 50% by weight of the powder mix of Example 3 to 50% by weight of sodium silicate.

Example 7 A gel-like composition was produced by adding 20% by weight of the basic powder mix of Example 5 to 80% by weight of sodium silicate.

Example 8 A powder mix of 70% by weight of low melting rit (450 degrees C) and devitrifying frit (700 degrees C) in the ratio of 3:7 and 30% by weight of hydrated magnesium calcium carbonate was prepared and then added to phenolic resin in the weight ratio of 3:7 to produce a mouldable material.

Example 9 Dough moulding compounds for use wir glass fibre reinforcement were prepared based on phenolic resin and on polyester resin. In both cases a powder mix of 20% by weight frits (low and high melting in a ratio of 3:7) and 80% by weight of hydrated magnesium calcium carbonate were added to the resin.

Example '0 sealant paste was produced from the following ingredients in the amounts stated: Mica powder (char agent) 10X by weight Ammonium polyphosphate 10 by weight Composition of Example 5 70 by weight Inorganic gelling agent 10% by weight Example il A resilient sealant was produced in the same way as in Example 10 except that polyvinyl acetate was used instead of sodium silicate.

Claims

1. A fire-retardant composition comprising two or more frits capable of melting progressively as the temperature rises under fire conditions, one of the said frits being a relatively low-melting frit and another of the said frits being a relatively highmelting devitrifying frit.

2. A composition according to Claim 1 wherein the frits melt within the range from about 450 degrees C to about 1000 degrees C.

3. A composition according to Claim 2 comprising (i) a relatively low-melting frit that starts to melt at about 450 degrees C and (ii) a devitrifying frit that starts to melt at about 700 degrees C.

4. A composition according to any of the preceding claims wherein the weight ratio of low-melting frit to high-melting frit is in the range from 1:9 to 1:1.

5. A composition according to Claim 4 wherein the weight ratio of low-melting frit to high-melting frit is about 3:7.

6. A composition according to any of the preceding claims further comprising an intumescent substance.

7. A composition according to Claim 6 wherein the intumescent substance is alumina trihydrate or hydrated magnesium calcium carbonate.

8. A composition according to -Claim 6 or Claim 7 wherein the proportion of frits is from 15% to 50% by weight of the total of frits and intumescent substance.

9. A composition according to any of the preceding claims further comprising ceramic fibre or powder.

10. A composition according to any of the preceding claims further comprising basalt fibre or powder.

11. A composition according to any of the preceding claims further comprising sodium silicate.

12. A composition according to any of Claims 1 to 10 further comprising a phenolic or polyester resin.

13. A composition according to any of Claims 1 to 10 further comprising polyvinyl acetate.

14. A fire-retardant composition as claimed in Claim 1 and substantially as described herein with reference to any one of Examples 1 to 4.

15. A fire-retardant composition as claimed in Claim 1 and substantially as described herein with reference to any one of Examples 5 to 11.

16. A method of providing or enhancing fire-retardant properties of a material or composition comprising adding to said material or composition a fire-retardant composition as claimed in any of Claims 1 to 5.