CA1042597A - Heat resistant and fire-proof synthetic resin material containing inorganic substances and process of producing thereof - Google Patents

Abstract

An organic material containing inorganic polymers or monomers which are interconnected with molecules of organic high molecular weight organic compounds. Such a material is useful in the ceramic industry including the manufacture of f?rnaces of a heat resistant ceramic barrier or coating material, of impregnating material and bonding agents. It is also suitable for producing a fire-proof or refractory material which is capable of being molded into a desired configuration such as a plate. The material is heat resistant and fire proof and comprises a synthetic resin and an inorganic substance dispersed in the resin material and capable of generating gases when heated.

Description

~04Z597 This invention relates to a novel fire-proof organic material which is produced by a process whereby heat resistant and fire-proof properties are improved. More particularly, the invention relates to a heat resistant synthetic material contain-ing an inorganic substance characterized by the fact that it comprises a mixture of a synthetic resin material and a high molecular weight inorganic substance or a porous inorganic substance which are cross-linked to each other. The invention also relates to a process of producing this product.
More particularly, the invention relates to a heat- ;-resistant or fire-resistant material comprising a synthetic thermosetting resin foam having dispersed therein (a) a salt of -~
boric acid containing water of crystallization or a salt of silicic acid containing water of crystallization other than an aluminium-containing salt of silicic acid, and (b) a naturally- ~ ~ ~
occurring aluminium-containing mineral other than alumina and ~ -other than the trihydrate of alumina, the ratio of the resin to component (a) to component (b) ranging between 100:10:3 to 100:300:300.
The new material of this invention can be considered as an inorganic substance in which inorganic polymers or monomers are interconnected with the molecules of high molecular weight -~
organic compounds. This type of material is useful in many industrial fields such as in the ceramic industry including the manufacture of furnaces, of heat resistant ceramic barriers or coating materials, of impregnating materi als and bonding agents.
The material is also suitable for the production of fire-proof or refractory structures which are capable of being molded into a desired configuration such as plates, especially for light weight fire-proof material of the type used in buiLdings.
In generàl, this invention also relates to an improved process of producing a foamed synthetic resin.
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It is well known to produce a foamed synthetic resin by reacting linear or branched-chain high and low molecular weight compounds upon gradual addition of a polyisocyanate or boric acid. However, this known process has the disadvantages that special and large device and a special technique are required for pouring and foaming and that there are many dominant factors in the process of mixing each component.
The invention relates to a process of mixing the components together by using a novel static mixer having spiral ~ ;' . -.

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,'," ' ' :' ~ ~ '. '` ' ",;. , ' '; . , guide vanes to produce a foamed synthetic resin material having a structure consisting of components which are interconnected together by means of physical and chemical bonds.
It is well known that the physical properties of a high molecular weight foamed material consisting of inorganic foam dispersed in a synthetic resin will be significantly modified and improved by a suitable heat treatment.
The gist of this invention resides in the production of a material on whose surface a glass-like layer is formed when it is heated at a high temperature. More particularly, the -- ~ -invention resides in the production of a heat resistant binding -agent which can advantageously be used with a composition which is capable of being hardened when mixed with water. The invention also resides in the production of a coating material or a layer -~
of foaming material which can form a layer having heat and flame resistant properties when applied at the surface of a board of inorganic substances or a panel of organic materials or sheet -materials for the production of laminated board or panels.
The porous synthetic resin material is light and has high plasticity so that especially when it is formed into a hard foam, it is useful as various kinds of structural members and auxiliary structural members for the building industry.
Accordingly, this invention may be featured by the manu-facture of a flame-proof material which is capable of being formed into a panel, sheet or square timber having the merits resulting both from the effective physical properties of inorganic ;
substances and the properties of organic substances described above, the material being manufactured by mixing a suitable synthetic resin with one or two kinds of suitable inorganic substances separately or simultaneously, based on the estimated mechanism of foaming.

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Another feature of this invention is to provide an improved process of and device for producing a material as descnbed above.
Generally speaking, a polymeric material comprising particles or short fibers of inorganic substances interconnected within the cellular structure of a foamed polymer mainly consist-ing of a synthetic resin has excellent physical properties caused by the reinforcement of the added inorganic substances together with the desirable physical properties such as the plasticity of the organic substances.
Accordingly, the high molecular weight organic material containing inorganic substances is extremely valuable for use in many industries, especially in buildings and other construction, in the form of panel, plate, square or round timber and laminated panel and also as the material for inner or outer finishing.
A primary object of this invention, therefore, is to provide a synthetic resin material containing inorganic substances having excellent physical properties for use as the material for buildings or other constructions.
For the purpose of usage, it should be said that materials for constructions having good flame-proof property at a high temperature are desirable. However, synthetic resins themselves are poor in heat resistivity and weather durability as compared with wood, metal and ceramics, as is well known in the art. Despite the above various synthetic resin materials are widely used around us due to their good plasticity and many attempts have been made to improve further their physlcal ~ -properties. In fact, many proposals and studies have been published.
Considered on the point of view of their flame-proof property, the synthetic resins are classified among those which .. ,~ .

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, :' ' ' , ~()4Z597 are hardly infla~mable and those which are incombustible type.
The former will continue to burn in contact with a flame so that it cannot be considered as the perfect fire-proof material, and the latter will not burn when left alone. Furthermore, the material of the latter type can be classified as a self . . .
extinguishable type which forms at the surface thereof an incombustible and heat-resistant layer when in contact with an `
atmosphere maintained at high temperature. The material can also be considered incombustible in the sense that it is stable to ~ ~-~
10 heat due to its inorganic material like structure. However, it -~
is a strict requirement to obtain a material which is fully stable at very high temperature and which comprises an organic substance as the main component.
Accordingly, another object of this invention is to provide an unexpensive incombustible synthetic resin material which can produce a heat resistant layer on the surface of the material at a high temperature.
A further object of the present invention is to provide a heat resistant and fire-proof synthetic resin material compris-ing a synthetic resin and an inorganic substance dispersed in ;
said resin material and capable of generating gases when heated.
A further object of this invention is to provid~Q board -materials for buildings including incombustible siding materials -~
for residences and various kinds of laminate panels.
According to this invention, there is provided the above-described type of board or panel which can easily be produced by using a simple apparatus.
A still further object of this invention is to provide , a novel adiabatic material in the form of a pipe, square or round timber which is capable of being produced on an industrial scale. ~-Considering the prior art, there are provided many , processes of producing a foamed material by adding a foaming agent to a desired synthetic resin, and there are also many kinds of foaming agent for use in the aforementioned process.
These artificial foam materials may be classified into those comprising high molecular weight organic compounds as the base and those which are inorganic. The former are composed of --polyethylene, polystyrene or polyurethane and the latter consists of a concrete foam and glass foam. One of the inorganic-foam material is concrete foam with independent cells. It comprises a polymer of a double salt of a cement and silicon dioxide and aluminum hydroxide as a film former. This type of polymer is different from the plastics foam.
The above-described glass foam is a refractory material produced by adding a small amount of powdered carbon black as a foaming agent to a mass of powdered glass, uniformly mixing the components with one another, heatlng the mass in a foaming mold foaming, cooling slowly and then withdrawing the product from the mold. In this case, antimony trioxide, potassium sulfate or ~ -borid acid may be added in order to balance the sintering speed of the glass and the rate of foaming is controlled by perform- `~
ing smoothly the decomposition of the foaming agent. However, the process is used only for the production of a foamed material mainly consisting of glass.
On the other hand, this invention contemplates to provide a prQcess of producing a novel and useful adiabatic resin material containing a high molecular weight inorganic substance which comprises adding to a synthetic resin a high molecular weight inorganic substance including boric acid and salts thereof and silicic acid and salts thereof, and or one or more kinds of inorganic foamable substances such as A12O3 and - minerals containing A12O3.

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. . , ~ , Examples of the synthetic resin used in this invention includes thermoplastic resins such as vinyl acetate resin, acrylic resin, polyvinyl alcohol, polystyrene, polyethylene, polypropylene and polyamide, and thermosetting resin such as condensation products of melamine, urea, phenol and epoxy resin, silicone resin, polyurethane and xylene resin.
The adiabatic material of this invention is characteri-zed by the fact that it comprises the synthetic resin as described above and boric acid, silicic acid or derivatives therefrom.
This material is superior in terms of antidefacement, antishock, hardness and dimension stability at normal temperature and has improved flame-proof ability due to the fact that a ceramic layer is produced on its surface at a high temperature. Also boric acid or derivatives therefrom generate gases at a higher temperature and silicic acid or derivatives therefrom generate -gases at even higher temperature.
For example, when boric acid or derivatives therefrom are added to a raw material containing a polyurethane resin, at ~-, the stage when in accordance with this invention the foaming reaction takes place, the resultant resin will be significantly -improved in its physical properties. For example, the material obtained is improved with respect to its antidefacement property, antishock property, hardness and dimension stability and shows an excellent flame-proof ability resulting from a ceramic layer formed at its surface. The material is derived from the dehy~ion reaction of boric acid or its derivatives, even though the poly-urethane will carbonise. When the material is further heated to a higher temperature, although the polyurethane resin produces a thermal decomposition, the fire-proof property can be maintained due to the fact that boric acid or its derivatives generate gases by releasing its crystallization water to combine the particles of ~ 6 -~ ,. ~

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~04ZS97 the material and to fill up the space therebetween. The tempera-ture of thermal decomposition of boric acid is 200 ~V300C, while the decomposition temperatures of the salts of boric acid, such as sodium borate, copper borate, lead borate and zinc borate are ~50 ^J700~C.
Similarly, when silicic acid or derivatives therefrom are added to the raw material containing a polyurethane resin, the same results will be expected. Furthermore, it is experimen-tally proved that the material containing particles of pearlite or other inorganic heat resistant materials or alumina clay minerals will endure a temperature of 1000C or more.
The material of this invention may contain phosphoric acid or phosphate such as sodium phosphate, potassium phosphate, ~-ammonium phosphate, calcium phosphate, magnesium phosphate and aluminum phosphates such as AlPO4, Al(H2PO4)3, Al(PO3)3 and the like. ~-Salts of silicic acid which can be used according to this invention include sodium silicate, potassium silicate, calcium silicate, copper silicate, zinc silicate and the like.
Similarly, examples of alumina containing minerals include -pearlite (75% SiO2, A12O3), vermiculite (water containing silicate comprising A12O3, Fe and Mg), agalmatolite (pyroferrite contain-ing 28.3% A12O3, 66.7% SiO2 and 5% H2O, for example), kaolin (a clay of the selicite series represented by the general formula A12O3 2sio2 2H2O and comprising 39.5% A12O3, 46.5%
SiO2, 14.0% H2O, for example), selicite, clay and hedenbergite.
A suitable clay includes those containing 36.4% of A12O3, 47-9% of SiO2, 1~8% of F2O3, 0.8% of CaO, 0.~% of MgO and 12.3%
of H2O. Furthermore, examples of suitable borates are potassium borate, sodium borate, magnesium borate, calcium borate, copper borate, lead borate and zinc borate.

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1~:)4Z597 In this invention, both thermoplastic and thermosetting resins are used, the former including polyvinyl acetate, and acrylate resin, polyvinyl alcohol, polystyrene, polyethylene, polypropylene and polyamide, and the latter a melamine resin, an urea resin, a phenol resin, an epoxy resin, a silicone resin, polyurethane, a xylene resin and the like.
Of course, the fillers added to the organic substance may include hydraulic substances which are produced through a suitable heating process such as a cement and plaster, and such substances can be used in lieu of the minerals described above.
This invention will be more fully understood from the following specific Examples, in which all parts are given by weight.

100 parts of an emulsion of polyvinyl chloride, 30 parts of aluminum phosphate, 30 parts of aluminum oxide and 30 parts of water were mixed in a mixer at 60C for 30 minutes and then poured into a mold. After heating at 100C for 40 minutes followed by slow cooling the foamed article was withdrawn from ~-~
the mold.

In a mixer 100 parts of polyethylene, 30 parts of ~~
pearlite particles, 40 parts of aluminum phosphate and 30 parts of water were mixed and the mixture obtained was heated in a mold at 300C for 20 minutes for foaming. The molded article was taken out of the mold after slow cooling for annealing.

100 parts of polystyrene, 25 parts of powdered agal-matoIite, 30 parts of aluminum oxide and 30 parts of water were mixed in a mixer at a temperature of 280C for 20 minutes and poured into a mold and then heated to a temperature of 200C for 7~

`' iO4ZS97 25 minutes. The molded article was taken out of the mold after slow cooling.

100 parts of polyurethane, 25 parts of vermiculite, 30 parts of sodium phosphate, 30 parts of water and 10 parts of a glass wool were mixed at 70C for 25 minutes in mixer and the --mixture was pressed at 250C for 35 minutes to form an article.
The properties of the articles obtained in Examples 1 to 4 are shown in the following Table 1.

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Example 1 Example 2 Example 3 Example 4 ~-Specific ~ravity 0.12-0.14 0.14-0.16 0.15-0.17 0.16-0.18 (g/cm ) Stretch Strength 8-10 7-9 9-10 8-11 (kg/cm2) Combustibility Self-extin- Incombusti-Incombusti-Incombusti-guishable ble ble ble Tolerance Durable to Durable to Durable to Durable to Alkali and Alkali and Alkali and Alkali and Weak Acid Acid Acid Acid Weather No Change No Change No Change No Change Durability After After After After Outdoor Outdoor Outdoor Outdoor Exposure Exposure Exposure Exposure - -for for for for 12 months 15 months 15 months 15 months Heat Resistivity 1810 1330 1340 1350 ( C ) :

-100 parts of polyethylene, 30 parts of aluminum oxide, 10 parts of chromic acid, 20 parts of sodium borate and 30 parts ~;
of aluminum phosphate were mixed in a mixer at 70C for 30 minutes and were transferred into a mold of a nickel containing alloy and then heated at a temperature of 200C for 30 minutes to foam it. The foamed article was taken out of the mold after being annealed.

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, ~04ZS97 100 parts of polyethylene, 30 parts of p~lite particl~

20 parts of phosphoric acid, 25 parts of ammonium chromate and 20 parts of sodium borate were mixed in a mixer at 50C for 40 minutes and heated at 300C during 20 minutes for foaming.

The resultant article was withdrawn from the mold after being -annealed.

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100 parts of polystyrene, 35 parts of ammonium phosphate, 30 parts of aluminum chromate, 10 parts of chromic acid, 20 parts of sodium borate, 30 parts of l'shiras balloonll (hollow glass particles) and 10 parts of asbestos wool were mixed in a mixer at 60C for 40 minutes and the mixture was pressed with an oil -press. The pressed body was then heated to a temperature of ~
150C during 40 minutes. ;
The articles obtained~in Exampl~ 5 to 7 had the proper-ties given in Table 2 below.

Example 5 Example 6 Example 7 Specific Gravity (g/cm3) 0.13-0.15 0.14-0.16 0.15-0.16 `
Stretch Strength ~kg/cm2) 8 - 11 7 - 10 9 - 11 Combustilibity Self-ex- Incombus- Incombus-tinguish- tible tible able Tolerance Durable to Durable to Durable to Alkali and Alkali a~d Alkali and Weak Acid Acid Acid Weather Durability No Change No Change No Change After After After Outdoor Outdoor Outdoor -Exposure~ Exposure Exposure for for for 12 months 15 months 15 months -Heat Resistivity (C) 1400 1450 1500 '~ - 10-, . ,, ' ~ ' : ' . .
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Air was blown into a mixture of 100 parts of molten polyethylene and 40 parts of pearlite particles to form an article containing small cells enclosing air.

Air was blown into a mixture of 100 parts of molten polyethylene and 40 parts of borax and the foamed mixture was molded into a desired configuration after which it was heated to -180 to 300C. During this treatment, blowing was performed by releasing and evaporating the water of crystallization of borax.

Air was blown into a mixture of 100 parts of aluminum phosphate, 40 parts of diatomaceous earth, 20 parts of sodium borate and 30 parts of water in order to mix the ingredients together. Inorganic polymers were formed by heating the mixture at 60 to 150C. The mass obtained contained small cells of air each having a diameter of 0.8 to 1.2mm and had a specific gravity -of 0.40 to 0.45 g/cm3.

Nitrogen was blown into a mixture of 100 parts of polyethylene, 40 parts of ammonium phosphate and 20 parts of sodium borate in order to mix the ingredients together, after which heating was carried out at 60 to 150C and then the mixture was cooled. The mass obtained had cells each having a diameter of 1.3 to l.5r~ and th~ ~peciiic gravity is 0.25 to 0.30 g/cr3.

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Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A heat-resistant or fire-resistant material comprising a synthetic thermosetting resin foam having dispersed therein (a) a salt of boric acid containing water of crystallization or a salt of silicic acid containing water of crystallization other than an aluminium-containing salt of silicic acid, and (b) a naturally-occurring aluminium-containing mineral other than alumina and other than the trihydrate of alumina, the ratio of the resin to component (a) to component (b) ranging between 100:10:3 to 100:300:300.

2. A material according to claim 1, wherein the salt of boric acid is potassium borate, sodium borate, copper borate, lead borate or zinc borate.

3. A material according to claim 1, wherein the salt of silicic acid is sodium silicate, potassium silicate, calcium silicate, copper silicate or zinc silicate.

4. A material according to claim 1, wherein the aluminium-containing mineral is an aluminosilicate.

5. A material according to claim 4, wherein the alumino-silicate is vermiculite, sericite, kaolin, agalmatolite or mica.

6. A material according to claim 1, 2 or 3, wherein the aluminium-containing mineral is obsidian or other volcanic glass, or hedenbergite.

7. A material according to claim 1, the synthetic resin having additionally dispersed therein phosphoric acid or a phosphate.

8. A material according to claim 7, wherein the phos-phate is sodium phosphate, potassium phosphate, ammonium phos-phate, calcium phosphate, magnesium phosphate or an aluminium phosphate.

9. A material according to claim 1, the synthetic resin having additionally dispersed therein Portland cement, plaster or other hydraulic material.

10. A material according to claim 1, 2 or 3 wherein the synthetic resin is polyvinyl acetate, an acrylic resin, polyvinyl alcohol,polystyrene, polyethylene, a polyamide, a melamine resin, a urea resin, a phenolic resin, an epoxy resin, a silicone resin, or a polyurethane.