JP2889127B2 - Flame retardant and refractory material using it - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for making a paper or a wood, for example, flame-retardant by applying or impregnating the same.

[0002]

2. Description of the Related Art Various types of flame retardants have been developed for making them flame-retardant by coating or impregnating them on the surface of a combustible material such as wood or cardboard. Among them, a flame-retardant urea-based and / or melamine-based amino resin as a main component, and by adding a water-soluble inorganic compound thereto, a ceramic foam layer having excellent heat resistance when exposed to a flame. What is formed is known. (JP-A-4-
93373).

However, since this flame retardant gels at around 10 ° C. even before curing, the workability when applying or impregnating the substrate is reduced, and furthermore, after curing, There is a problem that the coating film surface becomes sticky due to moisture absorption.

[0004] Asphalt felt using asbestos or rock wool is generally known as a refractory material used for building interiors, but these refractory materials are lightweight and relatively inexpensive, but have an adverse effect on the human body. To replace such conventional refractory materials,
Development of a lightweight, inexpensive, refractory material that is safe for the human body has been desired.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances. Instead of the above-described conventional flame retardant, a flame retardant which is stable and inexpensive in terms of hygroscopicity and viscosity is provided. It is an object of the present invention to further improve the conventional flame retardant while providing the same. It is another object of the present invention to provide a lightweight, inexpensive, and fire-resistant material that is safe for the human body by using a flame retardant having such excellent characteristics.

[0006]

Means for Solving the Problems The present inventors have intensively studied to develop a new flame retardant which can replace the conventional flame retardant as described above, and to further improve the conventional flame retardant. As a result, by using a flame retardant having a composition as described below, stickiness of the coating film surface due to moisture absorption and a change in viscosity based on temperature can be suppressed, and it can be manufactured at a lower cost than conventional ones. I found the fact. In addition, the present inventor can increase the amount of the flame retardant and reduce the weight of the flame retardant layer by coating the surface of the granules made of a predetermined material with the above-described flame retardant, as well as the filler and the like. It has been found that a granular refractory material suitable for the present invention can be obtained. The present invention has been made based on this finding.

That is, the first flame retardant according to the present invention is a mixture of sodium silicate, oxide ceramic, inorganic filler, carbide ceramic, nitride ceramic, silicon dioxide-containing compound, and water. . And
20-60 wt% sodium silicate, 1-15 wt% oxide ceramic, 5-25 wt% inorganic filler,
4-20 wt% carbide ceramic, 4-20 wt% nitride ceramic, 5-25 silicon dioxide containing compound
wt. and 5 to 25 wt% of water, preferably 42 wt% of sodium silicate, 5 wt% of oxide ceramic, 14 wt% of inorganic filler,
5wt% carbide ceramic, 5w nitride ceramic
t%, 16 wt% of a silicon dioxide-containing compound, and 13 wt% of water are mixed. Further, titanium oxide as an oxide ceramic, at least one selected from the group consisting of talc, clay, calcium carbonate, and mica as an inorganic filler, silicon carbide as a carbide ceramic, silicon nitride as a nitride ceramic Is mixed with at least one selected from the group consisting of pumice powder, perlite, diatomaceous earth, and mica powder as a silicon dioxide-containing compound.

Further, the second flame retardant according to the present invention is obtained by mixing sodium silicate, silicon dioxide, and water. And 40-60 sodium silicate
wt%, 10-40 wt% of silicon dioxide, and 1 of water
0 to 20% by weight, preferably 54% by weight of sodium silicate and 19% by weight of silicon dioxide.
% And 17 wt% of water.

Further, the present invention provides the first or second flame retardant material on any surface selected from the group consisting of a combustible material, a nonflammable material, a quasi-nonflammable material, a flame retardant material, and a quasi-flame retardant material. And a refractory material having a flame retardant layer formed thereon.

Further, the present invention provides a foamed resin material, a wooden material,
And the periphery of the granular material made of any one of the ceramic material and the first or second flame retardant, and a fire retardant layer is formed on the periphery of the granular material.

[0012]

The sodium silicate, oxide ceramic, carbide ceramic, nitride ceramic and silicon dioxide-containing compound contained in the first flame retardant form a flame retardant layer when mixed and cured. It becomes a non-combustible ceramic layer when exposed to a flame. Titanium oxide as oxide ceramic, silicon carbide as carbide ceramic, silicon nitride as nitride ceramic, pumice powder as silicon dioxide containing compound,
Perlite, diatomaceous earth, and mica powder can be used. The inorganic filler functions as a bulking agent having flame retardancy when mixed, and specifically, clay, calcium carbonate, and mica, which are fine powders such as talc and hydrous silicate minerals, can be employed. Water is added as a solvent for the sodium silicate. Sodium silicate exhibits tackiness by adding water, so it also functions as a binder for other component particles, and the viscosity can be easily adjusted by appropriately adjusting the amount of water.

If necessary, silica (silicon dioxide), alumina, mica or the like may be added as an auxiliary agent for providing flame retardancy. In addition, since the compound itself containing the carbide ceramic or silicon dioxide contained in the flame retardant itself is gray, the entire flame retardant also has a gray color. And chromium oxide (in the case of green) may be added as appropriate, and the addition amount is preferably 2% to 5%. To obtain a color other than the above, a commonly used aqueous pigment is appropriately added.

Further, sodium silicate, silicon dioxide,
The second flame retardant in which water and water are mixed can provide a colorless and nearly transparent flame retardant layer, particularly by adding silicon dioxide. That is, silicon dioxide is in a white powder state before mixing, but the entire flame retardant becomes substantially transparent when sodium silicate and water are mixed and dried, so that hue adjustment when coloring is facilitated. . It should be noted that sodium silicate, as in the case of the first flame retardant, exhibits tackiness by being mixed with water to form a flame retardant layer. The viscosity of the entire fuel material can be easily adjusted. Also, silicon dioxide functions as a material which gives flame retardancy to the flame retardant layer together with transparency.

The reason why the numerical range of each of the components contained in the first or second flame retardant is limited to the above range is as follows. That is, if the content of each component is less than the lower limit, the function of each component will not be sufficiently exhibited, and the formation of the flame retardant layer and its flame retardant effect will be affected. If the content of each component is more than the upper limit value, it is not only uneconomical, but also the viscosity becomes unstable and the workability is hindered.

The present invention also relates to paper, cardboard, wood,
Inflammable materials such as brick, asbestos slate, aluminum, etc., quasi-non-combustible materials such as gypsum board, wood wool cement, etc. By applying it to the surface of a flammable material or a quasi-flame-retardant material such as a reinforced polyester or a rigid vinyl chloride plate with a net, a refractory material having various characteristics can be obtained.

That is, for example, iron as a noncombustible material is 40
Although it is deformed by the heat of about 0 ° C., it can be prevented from being deformed by heat even when exposed to a flame of about 1500 ° C. by applying the flame retardant material according to the present invention. Furthermore, if the present flame retardant is applied or impregnated to a folded cloth, nonwoven fabric, glass fiber, or the like to fix the folded state, it is possible to obtain a refractory material having a curved surface shape suitable for various uses. Become. Furthermore, if the refractory material is applied to the surface of a foamed resin material made of styrene foam, a refractory material that is lightweight and inexpensive and can be freely set in thickness and shape can be obtained. The refractory material using such a foamed resin material has a refractory layer having a predetermined thickness, so that the foamed resin material melts even when exposed to a flame, but does not burn. Can be prevented.

Further, when the surface of the granular material made of a predetermined material is covered with the above-described flame retardant, the amount and weight of the flame retardant can be increased. That is, for example, when obtaining a refractory material as described above, an appropriate amount of lightweight granules are mixed in the flame retardant according to the present invention and cured to increase the flame retardant effect without substantially reducing the flame retardant effect. By forming a reduced and lightened flame retardant layer, or by curing the flame retardant on the surface in a state of being dispersed without aggregating each of the mixed granules, a granular refractory material is formed. Or get it. As the material of the granules, foamed resin materials such as styrofoam and urethane foam, wood materials such as cork, wood chips, and granular pulp can be adopted.Furthermore, if non-combustible materials such as ceramic materials are used, flame retardancy can be further improved. Can be. The use of a porous ceramic material can further reduce the weight of the entire flame retardant layer. As such a lightweight non-combustible material, other pumice or porous artificial stone particles can be used. . The shape of the particles is spherical, pellet,
Beads, irregular shapes, and the like can be appropriately selected. As a method for producing irregular-shaped particles, for example, a styrene foam block may be pulverized by a pulverizer.

When an appropriate amount of light-weight particles is mixed into the flame retardant, the flame retardant before curing can be given an appropriate fluidity and lightness, and the amount of the whole flame retardant can be increased. For example, it becomes easy to apply a flame retardant to the surface of the object by a spraying method using compressed air. On the other hand, when the flame retardant on the surface is hardened in a state of being dispersed without aggregating the respective particles, particularly in the case of the flame retardant containing sodium silicate, the amount of water to be added is adjusted. Thus, the viscosity of the entire flame retardant can be adjusted, so that the thickness of the flame retardant layer on the substrate surface can be adjusted. That is, for example, when the viscosity is increased by adding a small amount of water, the thickness of the flame retardant layer increases. Then, by appropriately filling such a granular refractory material into a hollow body having a flexible outer skin having a desired shape, for example, a lightweight material having appropriate flexibility and deformability suitable for automobiles and aircrafts. Various interior materials and components can be easily obtained.

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below. Examples 1 to 5 correspond to a first flame retardant, and Examples 6 to 9 correspond to a second flame retardant.

Example 1 The components shown below were mixed and stirred to obtain an opaque gray flame retardant.

Sodium silicate 42 wt%, titanium oxide 5 wt%, talc 14 wt%, silicon carbide 5 wt%, silicon nitride 5 wt% ………… 5wt%, silicon dioxide …………… 16wt%, water ………… 13wt%,

The flame retardant was applied in various thicknesses to the surface of a 5 mm-thick plywood and dried, and then a thin acrylic resin solution was applied to the surface to form a water-resistant transparent film. Then, the flame of a gas burner was applied to this surface to examine its flame retardant effect. The results are shown in Table 1 below. The time in the table is a time measured until the back surface is burnt and smoke is generated, and only when the thickness is 0 mm, that is, when the flame retardant is not applied, the surface burns to generate a flame. The time until was measured. Gas burner temperature is 600 ~ 1500
° C.

[0026]

[Table 1]

The flame retardant according to the present invention is used by being applied to non-combustible materials, semi-non-combustible materials, flame-retardant materials and semi-flame-retardant materials, in addition to the plywood as a combustible material as described above. ,
The evaluation of the flame retardant effect shall be performed when using the most flammable material, which is the most flammable material.
Tests for flame retardant and semi-flame retardant materials were omitted. In other words, it is clear that, in the case of using non-combustible materials, quasi-non-combustible materials, flame-retardant materials, and quasi-flame-retardant materials, the flame retarding effect is further improved and the time in the table is further shortened. For example, when actually used as a building material, it is of course preferable to use a material applied to a nonflammable material, a quasi-nonflammable material, a flame-retardant material, or a quasi-flame-retardant material rather than a combustible material. Such an evaluation method of the flame retardant effect of the flame retardant of the present invention was applied to the following examples.

Example 2 The components shown below were mixed and stirred to obtain an opaque green flame retardant.

[0029] Sodium silicate ... 60 wt%, titanium oxide ... 1 wt%, clay ... 5 wt%, silicon carbide ... 4 wt%, silicon nitride ... ............ 4 wt%, pumice powder ... 11 wt%, water ... 13 wt%, chromium oxide (coloring material) ... 2 wt%,

Then, this flame retardant was applied to the surface of a cardboard having a thickness of 5 mm, and its flame retardant effect was examined in the same manner as in Example 1. The results are shown in Table 2 below.

[0031]

[Table 2]

Example 3 Each component shown below was mixed and stirred to obtain an opaque red flame retardant.

Sodium silicate 34 wt%, titanium oxide 15 wt%, talc 6 wt%, silicon carbide 5 wt%, silicon nitride 5 wt% ... 3 wt%, perlite ... 10 wt%, water ... 15 wt%, silica (hydrogen dioxide) ... 2 wt%, alumina ... 5 wt%, Mica …………… 3wt%, Bengala ……………… 2wt%

Then, this flame retardant was applied to the surface of a styrofoam plate having a thickness of 50 mm, and its flame retardant effect was examined in the same manner as in Example 1. The results are shown in Table 3 below. In addition, * mark in a table | surface shows the time until styrene foam burns up, and the part without * shows the time until styrene foam melt | dissolves without generating a flame or smoke under a flame retardant layer.

[0035]

[Table 3]

In the case of the first and second embodiments, the thickness is 0 m.
Except for the case of m, it was confirmed that the flame retardant applied to the surface was blackened by the flame of the gas burner, but did not ignite and no flame was observed. In the case of the styrofoam plate of Example 3, when the thickness of the flame retardant layer is 0 and 0.1 mm, the flame can be burned in several seconds to several tens of seconds, but the thickness is 0.5, 1, and 2 mm.
It was confirmed that it melted out without generating flame or smoke and no harmful combustion gas was generated.

Further, as Example 4 and Example 5, when the same test was performed by changing the composition and the composition ratio in Example 1 as follows, almost the same results as in Table 1 were obtained.

Example 4 ;

[000] sodium silicate 20 wt%, titanium oxide 5 wt%, calcium carbonate 25 wt%, silicon carbide 20 wt%, silicon nitride ............ 20 wt%, diatomaceous earth ... 5 wt%, water ... 5 wt%,

Example 5 ;

Sodium silicate 34 wt%, titanium oxide 3 wt%, mica 5 wt%, silicon carbide 4 wt%, silicon nitride 4 wt% ............ 4 wt%, mica powder ... 25 wt%, water ... 25 wt%,

Example 6 The following components were mixed and stirred to obtain a transparent flame retardant.

Sodium silicate 54 wt%, silicon dioxide 19 wt%, water 17 wt%

The flame retardant was applied in various thicknesses to the surface of a 5 mm-thick plywood and dried, and then a thin acrylic resin solution was applied to the surface to form a water-resistant transparent film. Then, the flame of a gas burner was applied to this surface to examine its flame retardant effect. The results are shown in Table 4 below. The time in the table is a time measured until the back surface is burnt and smoke is generated, and only when the thickness is 0 mm, that is, when the flame retardant is not applied, the surface burns to generate a flame. The time until was measured. The temperature of the gas burner was in the range of 600 to 1500 ° C. as in Example 1.

[0044]

[Table 4]

Example 7 The following components were mixed and stirred to obtain a transparent flame retardant.

Sodium silicate 40 wt%, silica 40 wt%, water 20 wt%

Then, this flame retardant was applied to the surface of a cardboard having a thickness of 5 mm, and its flame retardant effect was examined in the same manner as in Example 4. The results are shown in Table 5 below.

[0048]

[Table 5]

Example 8 The following components were mixed and stirred to obtain a transparent flame retardant.

Sodium silicate 60 wt%, silica 30 wt%, water 10 wt%

Then, this flame retardant was applied to the surface of a 50 mm thick styrofoam plate, and its flame retardant effect was examined in the same manner as in Example 4. The results are shown in Table 6 below.

[0052]

[Table 6]

In the case of Embodiments 4 and 5, the thickness is 0 m.
Except for the case of m, it was confirmed that the flame retardant applied to the surface was blackened by the flame of the gas burner, but did not ignite and no flame was observed. In the case of the styrofoam plate of Example 6, when the thickness of the flame retardant layer is set to 0 or 0.1 mm, it burns up in several seconds to several tens of seconds, but the thickness is 0.5 mm, 1 m
When it was set to m and 2 mm, it was confirmed that the resin melted out without generating flame or smoke and that no harmful combustion gas was generated.

Example 9 The following components were mixed and stirred to obtain a transparent flame retardant.

Sodium silicate 60 wt%, silica 20 wt%, water 20 wt%

Then, using this flame retardant, the above embodiment 8 was used.
When the same test was performed, substantially the same results were obtained.

Hereinafter, embodiments of the refractory material according to the present invention will be described.

Embodiment 10 FIG. 1 shows an example in which the surface of a lightweight granule is coated with a flame retardant to form a flame retardant layer. In the flame retardant having the composition described in Example 1 above, By mixing and agitating spherical styrofoam particles 1, 1,... Having a diameter of about 3 mm, the surface of each styrofoam particles 1, 1,. I made it. An appropriate amount of the particles coated with the flame retardant layer 2 is applied to the surface of a 2 mm-thick plywood 3 so as to have a predetermined thickness to form a surface layer 4, and an acrylic resin liquid is further applied on the surface layer 4. Refractory material 6 coated with water-resistant transparent film 5 by applying thinly
I got

The thickness of the surface layer 4 of the refractory material 6 was variously set, and a flame of a gas burner was applied to the surface of the refractory material 6 to examine the flame retarding effect in each case. The results are shown in Table 7 below. In addition, the time in a table | surface measured the time until a back surface burns and smoke is generated, and the temperature of the gas burner was made into the range of 600-1500 degreeC.

[0080]

[Table 7]

Further, the flame retardant effect was examined under the same conditions as in Example 1 except that a spherical porous ceramic material having a diameter of about 3 mm was used instead of the styrene foam granules in Example 10. The results are shown in Table 8 below.

[0082]

[Table 8]

Example 11 FIG. 2 shows an example of a wallpaper. As in FIG. 1, spherical particles of spherical polystyrene having a diameter of about 1 to 5 mm were included in the flame retardant described in Example 4 above. , 7,... Are mixed and agitated by spraying onto one surface of a twist-resistant paper 8 which has been subjected to a flame-retardant treatment with aluminum hydroxide, and has a surface layer 9 having a thickness of about 3 mm. Thus, a wallpaper 10 rich in three-dimensional effect was obtained.

The thickness of the surface layer 9 of the wallpaper 10 was set variously, and a flame of a gas burner was applied to the surface of the wallpaper 9 to examine the flame retardant effect in each case in the same manner as in Example 1. The results are shown in Table 9 below.

[0085]

[Table 9]

Further, the styrene foam granules were replaced with irregular shaped cork pieces having an appropriate size and shape, and the flame retardant effect was examined under the same conditions. The results are shown in Table 10 below.

[0087]

[Table 10]

From the results of Tables 7, 8, and 10, it was confirmed that the refractory material of Example 10 and the wallpaper of Example 11 had a sufficiently practical flame retardant effect. When the ceramic particles were used, the flame retardant effect was further improved as compared with Tables 7, 8, and 10.

Example 12 FIG. 3 shows an example of a granular refractory material. In the flame retardant having the composition described in the above Example 7, a spherical polystyrene foam particle 11 having a diameter of about 1 to 5 mm was used. .. Were mixed, and the flame retardant was hardened while stirring so that each particle did not agglomerate. Thereby, the granular refractory material 13 having the flame retardant layers 12, 12,... Having a thickness of about 1 mm on the surface of each granular material,
13 are obtained, and the expanded polystyrene particles 1
, And the acrylic resin liquid were mixed, and the mixture was cured with stirring to be coated with a water-resistant transparent film 5. As shown in FIG. 4, this granular refractory material 13, 13,... Is filled in an appropriate amount inside a vinyl chloride skin 15 in which a core material 14 is incorporated, and has an appropriate cushioning property. It is a lightweight, flame-retardant vehicle seat 16.

[0090]

As described above, the first flame retardant according to the present invention comprises sodium silicate, oxide ceramic, inorganic filler, carbide ceramic, nitride ceramic and silicon dioxide-containing compound as main components. Therefore, it is inexpensive, has low moisture absorption, and has a stable viscosity, as compared with a conventional flame retardant containing a urea-based and / or melamine-based amino resin precondensate and a water-soluble inorganic compound as main components. And viscosity adjustment can be easily performed only by adjusting the amount of water. Further, coloring can be easily performed by adding bengara, chromium oxide or the like as appropriate.

Since the second flame retardant according to the present invention is a mixture of sodium silicate, silica and water, it is possible to obtain a colorless and nearly transparent flame retardant layer at a lower cost than before. Can be.

Further, the third flame retardant according to the present invention is:
The base material mainly composed of urea-based and / or melamine-based amino resin precondensate is mixed with aluminum phosphate, water-soluble adhesive and water. If a water-resistant resin film is formed on this surface, a flame retardant excellent in weather resistance and water resistance can be obtained. Further, since the viscosity of such an adhesive before curing does not substantially change even when the temperature changes, the viscosity of the entire flame retardant is also stable, and the workability does not decrease.

In the present invention, since the surfaces of the granules are covered with the above-described flame retardant, the amount of the flame retardant can be increased without substantially reducing the overall flame retardant effect. The weight can be reduced, and a granular refractory material suitable for a filler can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a refractory material according to the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the refractory material according to the present invention.

FIG. 3 is a schematic cross-sectional view showing a refractory material having a flame retardant layer formed on a particle surface.

FIG. 4 is a schematic sectional view showing a vehicle seat filled with a refractory material according to the present invention.

[Explanation of symbols]

 1,7,11 Styrofoam granules 2,11 Flame retardant layer 3 Veneer board 8 Flame retardant paper 6,13 Fire resistant material

Continued on the front page (51) Int.Cl. ⁶ Identification code FI D21H 17/67 D21H 3/78

Claims (9)

(57) [Claims] 1. A sodium silicate, an oxide ceramic,
Inorganic filler, carbide ceramic, nitride ceramic,
A flame retardant obtained by mixing a silicon dioxide-containing compound and water. 2. A sodium silicate of 20 to 60% by weight,
1 to 15 wt% of oxide ceramic and 5 of inorganic filler
The flame retardant according to claim 1, wherein the flame retardant is a mixture of -25 wt%, 4-20 wt% of a carbide ceramic, 4-20 wt% of a nitride ceramic, 5-25 wt% of a silicon dioxide-containing compound, and 5-25 wt% of water. . 3. A composition comprising 42 wt% of sodium silicate, 5 wt% of oxide ceramic, 14 wt% of inorganic filler, 5 wt% of carbide ceramic and 5 wt% of nitride ceramic.
%, 16 wt% of a silicon dioxide-containing compound and 1 of water.
The flame retardant according to claim 1 or 2 which is mixed at 3 wt%. 4. Titanium oxide as an oxide ceramic,
Talc, clay, calcium carbonate, as inorganic filler
And at least one selected from the group consisting of mica, silicon carbide as a carbide ceramic, silicon nitride as a nitride ceramic, pumice powder as a silicon dioxide-containing compound, perlite, diatomaceous earth, and mica powder The flame retardant according to any one of claims 1 to 3, wherein at least one kind selected from the group consisting of a mixture of the above is mixed. 5. A flame retardant comprising a mixture of sodium silicate, silicon dioxide, and water. 6. A sodium silicate of 40 to 60 wt%,
10 to 40 wt% of silicon dioxide and 10 to 20 of water
The flame retardant according to claim 5, wherein the flame retardant is mixed in a wt% ratio. 7. The flame retardant according to claim 5, wherein 54 wt% of sodium silicate, 19 wt% of silicon dioxide and 17 wt% of water are mixed. 8. The flame retardant according to claim 1, wherein the surface is selected from the group consisting of a combustible material, a nonflammable material, a quasi-nonflammable material, a flame retardant material, and a quasi-flame retardant material. Refractory material with a fire retardant layer formed on it. 9. A periphery of a granule made of any one of a foamed resin material, a wood material, and a ceramic material is coated with the flame retardant according to any one of claims 1 to 7, and a flame retardant layer is formed thereon. Refractory material made.