JP2000291176A - Fire resistant panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the excellent fire resistant performance by laminating a metal plate on at least one surface of a fire resistant expansion sheet made of the resin composition including the neutralized thermal expansion graphite having a specified value of thermal expansion starting temperature. SOLUTION: A fire resistant expansion sheet (a) is composed of thermosetting resin, rubber material, neutralized thermal expansion graphite, phosphorus compound and inorganic filling agent. Quantity of blending of the neutralized thermal expansion graphite and the phosphorus compound is set at 20-200 pts.wt. in relation to 100 pts.wt. of the rubber material, and weight ratio between the thermal expansion graphite and the phosphorus compound is set at 0.01-9, and quantity of blending of the inorganic filling agent is set at 50-500 pts.wt. A zinc-iron plate (b) having 0.1-1.5 mm of thickness is laminated on a surface of the fire resistant expansion sheet (a) having 140-180 deg.C of expansion starting temperature and 0.3-5 mm of thickness so as to form a fire resistant panel, and this fire resistant panel is laminated on a back surface of a ceramic industrial siding and attached by the adhesive agent provided in the fire resistant expansion sheet (a) so as to form a fire resistant structure wall. Consequently, panels having excellent fire resistance and workability can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fireproof panel excellent in fire resistance and workability used as a building member such as a ceiling material, a floor material, a partition wall and the like.

[0002]

2. Description of the Related Art Building materials are required to have fire resistance, that is, a property that is not easily flammable by itself, has excellent heat insulation properties, and does not allow a flame to flow to the back surface. As a test method of fire resistance, there is a method of measuring the temperature of the back surface when the front surface is heated to about 1000 ° C. In building materials, it is required that the temperature of the back surface in this case be lower than about 260 ° C. Have been.

[0003] As such a building member having excellent fire resistance, a fire panel made of gypsum, perlite or the like is widely used. However, in order for these materials to exhibit sufficient fire resistance, it is necessary to increase the thickness, and there is a problem in workability.

Japanese Patent Application Laid-Open No. 61-1753 discloses a fire-resistant wall provided with a heat-expandable layer on the periphery.
However, this is mainly intended to prevent the flame from turning to the back surface by suppressing the generation of gaps at the joints due to shrinkage of the fire-resistant wall, and is inferior in heat insulation.

Japanese Patent Application Laid-Open No. 6-80909 discloses a method of spraying fine powder of a composition comprising a cement, a hydrated inorganic substance and the like. However, this method is inferior in workability because it requires on-site spraying work, and when the thickness is not uniform, sufficient fire resistance cannot be exhibited. Furthermore, since fine powder is scattered during construction, the effect on health is great.

[0006]

SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a fireproof panel excellent in fire resistance and workability.

[0007]

According to the first aspect of the present invention, there is provided a fireproof panel comprising a resin composition having an expansion start temperature of 140 to 180 ° C and containing a neutralized heat-expandable graphite. 0.3 to 5 mm thick fire resistant expansion sheet (a)
Characterized in that a metal plate (b) having a thickness of 0.1 to 1.5 mm is laminated on at least one surface.

[0008] The fireproof panel of the present invention is coated on the back surface of a wall material such as ceramic siding or metal siding,
It is a member for imparting fire resistance performance. The fire-resistant expansion sheet (a) has a performance of forming a fire-resistant heat-insulating layer by expanding due to heat at the time of fire. By the formation of the fire-resistant heat-insulating layer, heat is transmitted to the opposite side of the fire-resistant structure wall. And satisfy the fire resistance required as a building material.

[0009] The thickness of the fire-resistant expansion sheet (a) is 0.1 mm.
3-5 mm. If it is less than 0.3 mm, sufficient heat insulation may not be exhibited even if expanded, and if it exceeds 5 mm, workability when laminating to a wall material and producing a fire-resistant structure wall becomes poor. Refractory structure wall obtained, and thickened
The weight increases and workability deteriorates.

When the refractory expansion sheet (a) is heated to 300 ° C., the relationship between the thickness before heating (t) and the thickness after heating (t ′) is t ′ / t = 1. It is preferably 1 to 20. When the value of t '/ t is less than 1.1, the heat insulating property is deteriorated. When the value of t' / t is more than 20, the expanded shape cannot be maintained, and there is a possibility of peeling from the wall material. More preferably, t '/ t = 1.5 to 15. Further, when heated to 300 ° C., it is more preferable that the thickness (t ′) after heating is twice or more the thickness (t) before heating.

The fire-resistant expansion sheet (a) expands in the event of a fire to exhibit heat insulation performance, has an expansion start temperature of 140 to 180 ° C., and contains neutralized heat-expandable graphite. It can be obtained by molding the resin composition to be formed into a sheet shape.

The neutralized heat-expandable graphite is obtained by neutralizing a conventionally known heat-expandable graphite. The heat-expandable graphite is a natural scale-like graphite, pyrolytic graphite, powder such as quiche graphite,
Produced by treating with inorganic acids such as concentrated sulfuric acid, nitric acid, and selenic acid and strong oxidizing agents such as concentrated nitric acid, perchloric acid, perchlorate, permanganate, dichromate, and hydrogen peroxide. It is a graphite intercalation compound that is a crystalline compound while maintaining a layered structure of carbon.

The heat-expandable graphite obtained by the acid treatment as described above is further neutralized with ammonia, an aliphatic lower amine, an alkali metal compound, an alkaline earth metal compound, etc. And heat-expandable graphite. The aliphatic lower amine is not particularly limited, for example,
Monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like can be mentioned. The alkali metal compound and alkaline earth metal compound are not particularly limited, and include, for example, hydroxides, oxides, carbonates, sulfates, and organic acid salts of potassium, sodium, calcium, magnesium, barium and the like. .

The expansion starting temperature of the neutralized heat-expandable graphite is 140 to 180 ° C. If the temperature is lower than 140 ° C., expansion starts when kneading with the thermoplastic resin and / or the rubber substance, and the fire resistance decreases. If the temperature exceeds 180 ° C., expansion does not start until the ambient temperature becomes 180 ° C. That is, since it does not exhibit the heat insulating effect during this time, it is disadvantageous for coating a small-scale fire or a material having a low thermal conductivity. In the present invention, since the heat-expandable graphite having the expansion start temperature of 140 to 180 ° C. is used, the heat-insulating layer is quickly formed, which is advantageous in fire resistance performance. In particular, in a thin panel material as in the present invention, it is important that the heat insulating layer is formed early. Examples of the thermal expansion graphite having an expansion start temperature of 140 to 180 ° C. include “GRAFGuard # 160” manufactured by UCAR Carbon. In the present invention, the expansion start temperature is 140 to 1
You may mix and use the heat-expandable graphite which is 80 degreeC, and the heat-expandable graphite whose expansion start temperature is out of the said range.

The particle size of the neutralized heat-expandable graphite is preferably 20 to 200 mesh. When the particle size is smaller than 200 mesh, the degree of expansion of graphite is small, a predetermined refractory insulation layer cannot be obtained, and when the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large,
When kneaded with a thermoplastic resin and / or a rubber substance, dispersibility deteriorates, and deterioration of physical properties cannot be avoided.

The fire-resistant expansion sheet (a) is preferably a resin composition comprising the neutralized heat-expandable graphite, a thermoplastic resin and / or a rubber substance, a phosphorus compound, and an inorganic filler.

The thermoplastic resin and / or rubber substance is not particularly limited, and examples thereof include polyolefin resins such as polypropylene resins and polyethylene resins, poly (butene-1) resins, polypentene resins, polystyrene resins, and the like. Acrylonitrile-styrene-butadiene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, phenol resin, polyurethane resin, polybutene, polychloroprene, polybutadiene,
Examples include polyisobutylene and nitrile rubber.

Of these, halogenated resins such as chloroprene-based resins and chlorinated butyl-based resins have high flame retardancy by themselves, cross-linking occurs by a dehalogenation reaction by heat, and the strength of the residue after heating is low. It is preferable in terms of improvement. The thermoplastic resins and / or rubber materials exemplified above are very flexible and have rubber-like properties, so that they can be highly filled with phosphorus compounds, inorganic fillers, etc., and the resulting resin composition Things become flexible. In order to obtain a more flexible resin composition, a non-vulcanized rubber or a polyethylene resin is preferably used.

The above-mentioned thermoplastic resin and / or rubber substance is
They may be used alone or in combination of two or more. A blend of two or more resins may be used as the base resin in order to adjust the melt viscosity, flexibility, adhesiveness, and the like of the resin.

The thermoplastic resin and / or rubber material may be further crosslinked or modified within a range that does not impair the fire resistance performance of the fire resistant expansion sheet (a) of the present invention. The timing at which the thermoplastic resin and / or the rubber material is crosslinked or modified is not particularly limited. For example, a previously crosslinked and modified thermoplastic resin and / or rubber material may be used. Crosslinking or modification may be performed at the same time when other components such as a phosphorus compound or an inorganic filler are blended, or crosslinking and modification may be performed after blending other components with a thermoplastic resin and / or a rubber substance. May be performed.

The crosslinking method is not particularly limited.
Crosslinking methods usually used for thermoplastic resins and / or rubber substances, for example, crosslinking methods using various crosslinking agents and peroxides, and crosslinking methods using electron beam irradiation are exemplified.

The above-mentioned phosphorus compound is not particularly restricted but includes, for example, red phosphorus; various phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate; Metal phosphates such as sodium phosphate, potassium phosphate and magnesium phosphate;
Ammonium polyphosphates; compounds represented by the following general formula (1) and the like. Among these, from the viewpoint of fire resistance, red phosphorus, ammonium polyphosphates, and compounds represented by the following general formula (1) are preferable, and ammonium polyphosphates are more preferable in terms of performance, safety, cost, and the like. preferable.

[0023]

Embedded image

In the formula, R ¹ and R ³ are hydrogen, carbon number 1 to 1
6 represents a linear or branched alkyl group or an aryl group having 6 to 16 carbon atoms. R ² is a hydroxyl group, a linear or branched alkyl group having 1 to 16 carbon atoms, a linear or branched alkoxyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, Represents an aryloxy group represented by Formulas 6 to 16.

The flame retardant effect is improved by adding a small amount of the above-mentioned red phosphorus. As the red phosphorus, commercially available red phosphorus can be used, but from the viewpoint of moisture resistance, safety such as not spontaneously igniting during kneading, those obtained by coating the surface of red phosphorus particles with a resin are preferably used. .

The above-mentioned ammonium polyphosphates are not particularly restricted but include, for example, ammonium polyphosphate and melamine-modified ammonium polyphosphate. Of these, ammonium polyphosphate is preferably used from the viewpoint of handleability and the like. As a commercially available product, for example, "AP4" manufactured by Hoechst
22, "AP462", "Sumisafe P" manufactured by Sumitomo Chemical Co., Ltd., "Terage C60" manufactured by Chisso Corporation, and the like.

The compound represented by the above general formula (1) is not particularly restricted but includes, for example, methylphosphonic acid, dimethyl methylphosphonate, diethyl methylphosphonate, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, 2-methylpropyl Phosphonic acid, t-butylphosphonic acid, 2,3-dimethyl-butylphosphonic acid, octylphosphonic acid, phenylphosphonic acid, dioctylphenylphosphonate, dimethylphosphinic acid, methylethylphosphinic acid, methylpropylphosphinic acid, diethylphosphinic acid, dioctyl Examples include phosphinic acid, phenylphosphinic acid, diethylphenylphosphinic acid, diphenylphosphinic acid, and bis (4-methoxyphenyl) phosphinic acid. Among them, t-butyl phosphonic acid is expensive, but is preferable in terms of high flame retardancy. The phosphorus compounds may be used alone or in combination of two or more.

The inorganic filler is not particularly limited.
For example, metal oxides such as alumina, zinc oxide, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, and ferrites; calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, and the like. Hydrous inorganic substances; metal carbonates such as basic magnesium carbonate, magnesium carbonate, calcium carbonate, zinc carbonate, strontium carbonate, barium carbonate; calcium sulfate, gypsum fiber, calcium silicate, silica, diatomaceous earth, dawnite, barium sulfate, magnesium sulfate , Talc, clay, mica, montmorillonite, bentonite, activated clay, sepiolite, imogolite, sericite, glass beads, silica-based balloon, aluminum nitride, boron nitride, silicon nitride, carbon black, carbon balloon, charcoal powder , Graphite, potassium titanate, lead zirconate titanate, aluminum borate, zinc borate, molybdenum sulfide, silicon carbide, carbon fiber, glass fiber, slag fiber, stainless steel fiber, various metal powders, various magnetic powders, fly ash And dewatered sludge. Of these, the above-mentioned hydrated inorganic substances and metal carbonates are preferred.

Water-containing inorganic substances such as magnesium hydroxide and aluminum hydroxide are endothermic due to water generated by a dehydration reaction during heating, thereby suppressing a rise in temperature and obtaining high heat resistance. It is particularly preferable in that the oxide remains as an aggregate and acts as an aggregate to improve the strength of the residue. Magnesium hydroxide and aluminum hydroxide differ in the temperature range in which the dehydration reaction occurs, so that when they are used together, the temperature range in which the above-mentioned dehydration reaction exerts the effect of suppressing the temperature rise expands, and the more effective temperature rise suppression effect Can be played. From such a viewpoint, it is preferable to use both.

Metal carbonates such as calcium carbonate and zinc carbonate are considered to react with ammonium polyphosphate to promote expansion of ammonium polyphosphate when ammonium polyphosphate is used as the phosphorus compound. In addition, it acts as an effective aggregate and forms a residue having high shape retention after burning. Among the above-mentioned metal carbonates, alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate and strontium carbonate; and periodic table I such as zinc carbonate
Group Ib metal carbonates are preferred. Generally, an inorganic filler acts as an aggregate, and is considered to contribute to an improvement in residue strength and an increase in heat capacity. The inorganic fillers may be used alone or in combination of two or more.

The inorganic filler has a particle size of 0.5 to
100 μm can be used, and more preferably, about 1 to
50 μm. It is more preferable to use a combination of an inorganic filler having a large particle size and a filler having a small particle size. By using the inorganic filler in combination, it is possible to increase the packing while maintaining the mechanical performance of the sheet.

[0032] In addition to the thermoplastic resin and / or rubber substance, the phosphorus compound and the inorganic filler,
Polyhydric alcohols and the like may be added.

The polyhydric alcohol is a hydrocarbon compound having two or more hydroxyl groups in the molecule, and preferably has 1 to 50 carbon atoms. Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6
-Hexanediol, monopentaerythritol, dipentaerythritol, tripentaerythritol, neopentaerythritol, sorbitol, inositol,
Mannitol, glucose fructose, starch, cellulose and the like can be mentioned. The polyhydric alcohols may be used alone or in combination of two or more.

As the polyhydric alcohol, the ratio of the number of hydroxyl groups to the number of carbon atoms in the molecule [(number of hydroxyl groups) / (number of carbon atoms)]
Is preferably from 0.2 to 2.0, and more preferably [(number of hydroxyl groups) / (number of carbon atoms)] as represented by pentaerythritols, sorbitol, mannitol and the like is 0.7. ~ 1.5. Above all, pentaerythritols are most preferred because of their high hydroxyl group content and high carbonization promoting effect.

Polyhydric alcohols having a ratio of the number of hydroxyl groups to the number of carbon atoms in the molecule [(the number of hydroxyl groups) / (the number of carbon atoms)] in the range of 0.2 to 2.0 are dehydrated and condensed during combustion. To effectively form a carbonized layer. The above ratio [(number of hydroxyl groups) /
(Carbon number)] is less than 0.2, the decomposition of carbon chains is more likely to occur during combustion than dehydration condensation, so that a sufficient carbonized layer cannot be formed. Although it does not interfere with the formation of the layer, the water resistance is greatly reduced. When the water resistance is reduced, when the resin composition immediately after molding is water-cooled, the polyhydric alcohol is eluted or there is a problem that the polyhydric alcohol bleeds out depending on the temperature during storage of the molded article. .

Hereinafter, preferred examples of the resin composition constituting the fire-resistant expansion sheet of the present invention will be described with specific examples. As each material such as a thermoplastic resin and / or a rubber substance constituting the resin compositions 1 to 5 described below, those described above are used. First, as the resin composition 1 of the present invention, a thermoplastic resin and / or a rubber substance, a neutralized heat-expandable graphite, a phosphorus compound and an inorganic filler, and the neutralized heat-expandable graphite and The compounding amount of the phosphorus compound is 20 to 200 in total with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance.
Parts by weight, the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound [(neutralized thermally expandable graphite) / (phosphorus compound)] is 0.01 to 9, and the inorganic filler is Is 50 to 500 parts by weight based on 100 parts by weight of the thermoplastic resin and / or rubber substance, and the weight ratio of the inorganic filler and the phosphorus compound [(inorganic filler) / (phosphorus compound)] But a resin composition of 0.6 to 1.5.

Among the above-mentioned inorganic fillers, the above-mentioned hydrated inorganic material, the above-mentioned alkali metal, alkaline earth metal and metal carbonate of Group IIb metal of the periodic table, a mixture of the above-mentioned hydrated inorganic material and a mixture of the above-mentioned metal carbonate, etc. Is preferred.

The amount of the neutralized and thermally expandable graphite phosphorus compound is preferably 20 to 200 parts by weight in total with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance. If the amount is less than 20 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 200 parts by weight, mechanical properties are greatly reduced and the product cannot be used.

The amount of the inorganic filler is 50 to 100 parts by weight of the thermoplastic resin and / or the rubber substance.
500 parts by weight are preferred. If it is less than 50 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 500 parts by weight, the mechanical properties are greatly reduced, and it cannot be used. More preferably, it is 60 to 300 parts by weight. The weight ratio [(inorganic filler) / (phosphorus compound)] between the inorganic filler and the phosphorus compound is preferably from 0.6 to 1.5.

The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound [(neutralized heat-expandable graphite)
/ (Phosphorus compound)] is preferably from 0.01 to 9. The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound is
By setting it to 0.01 to 9, it is possible to obtain shape retention of combustion residues and high fire resistance. If the compounding ratio of the neutralized heat-expandable graphite is too large, the expanded graphite will be scattered during combustion, and a sufficient expanded heat-insulating layer cannot be obtained. On the other hand, if the mixing ratio of the phosphorus compound is too large, the formation of the heat insulating layer becomes insufficient, so that a sufficient heat insulating effect cannot be obtained.

The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound [(neutralized heat-expandable graphite) /
(Phosphorus compound)] within the above range of 0.01 to 9, when the compounding ratio of the neutralized heat-expandable graphite is large, a high expansion ratio can be obtained, but the shape retention is not sufficient. In this case, from the viewpoint of shape retention during combustion, the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound is:
0.01 to 2 is preferred. More preferably, 0.02-
0.3, and more preferably 0.025 to 0.2. When the blending amount of the neutralized heat-expandable graphite is 10
When the amount is less than parts by weight, shape retention is relatively good, and combustion residues do not collapse.

Although the mechanism of the fire resistance of the above composition 1 is not necessarily clear, it is considered that it develops as follows. That is, the heat-expandable graphite that has been neutralized expands by heating to form a heat-insulating layer, thereby preventing heat transfer. The inorganic fillers then contribute to an increase in heat capacity. The phosphorus compound has a shape-retaining ability of the expanded heat-insulating layer.

Next, as the resin composition 2 in the present invention, there may be mentioned a resin composition in which the inorganic filler in the resin composition 1 comprises an alkali metal, an alkaline earth metal and a metal carbonate of a metal of Group IIb of the periodic table. .

Although the mechanism of the fire resistance of the resin composition 2 is not necessarily clear, it is considered that the mechanism manifests as follows. That is, the decarboxylation and deammonification reactions are accelerated by the chemical reaction between polyphosphoric acid and carbonate generated from the phosphorus compound during heating. The phosphorus compound generates polyphosphoric acid and also functions as a binder for the foam film. Metal carbonates play an aggregate role.

Next, as the resin composition 3 in the present invention, the inorganic filler in the resin composition 1 is a metal carbonate of an alkali metal, an alkaline earth metal and a metal of Group IIb of the periodic table, and a hydrated inorganic substance and / or And those composed of calcium salts. The calcium salt is not particularly limited, and includes, for example, calcium sulfate, gypsum, calcium diphosphate and the like.

The total amount of the hydrated inorganic substance and / or calcium salt is preferably 1 to 70 parts by weight based on 100 parts by weight of the metal carbonate. If it exceeds 70 parts by weight, good shape retention cannot be exhibited.

Although the mechanism of the fire resistance of the resin composition 3 is not necessarily clear, it is considered that it develops as follows. That is, the decarboxylation and deammonification reactions are accelerated by the chemical reaction between polyphosphoric acid and carbonate generated from the phosphorus compound during heating. The phosphorus compound generates polyphosphoric acid and also functions as a binder for the foam film. Metal carbonates play an aggregate role. The hydrated inorganic substance and / or calcium salt is considered to play an aggregate role similarly to the metal carbonate.

Further, as the resin composition 4 in the present invention,
A thermoplastic resin and / or rubber substance, a phosphorus compound, a neutralized heat-expandable graphite, a polyhydric alcohol, and a metal carbonate of the above-mentioned alkali metal, alkaline earth metal and Group IIb metal of the periodic table. The total amount of the compound, the neutralized heat-expandable graphite, the polyhydric alcohol and the metal carbonate is equal to or less than the thermoplastic resin and / or the rubber substance 100.
50 to 900 parts by weight to the weight part of the polyhydric alcohol and the phosphorus compound [(polyhydric alcohol) /
(Phosphorus compound)] is 0.05 to 20, and the weight ratio of the neutralized heat-expandable graphite to the phosphorus compound [(neutralized heat-expandable graphite) / (phosphorus compound)] is as follows: , 0.
01 to 9, the weight ratio of the metal carbonate to the phosphorus compound [(metal carbonate) / (phosphorus compound)] is 0.01 to 5;
0 resin composition.

The mixing ratio of the phosphorus compound, the neutralized heat-expandable graphite, the polyhydric alcohol and the metal carbonate is based on 100 parts by weight of the thermoplastic resin and / or rubber substance. Preferably the amount is from 50 to 900 parts by weight. If the total amount of the above four components is less than 50 parts by weight, the amount of the residue after heating becomes insufficient, and a fire-resistant heat-insulating layer cannot be formed. Physical properties decrease. More preferably 100 to 700 parts by weight, even more preferably 2 to
It is 00 to 500 parts by weight.

The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound [(neutralized heat-expandable graphite)
/ (Phosphorus compound)] is preferably 0.01 to 9. By setting the weight ratio of the neutralized heat-expandable graphite to the phosphorus compound to 0.01 to 9, the shape retention of combustion residues and high fire resistance can be obtained. If the compounding ratio of the neutralized heat-expandable graphite is too large, the expanded graphite will be scattered during combustion, and a sufficient expanded heat-insulating layer cannot be obtained. On the other hand, if the mixing ratio of the phosphorus compound is too large, a sufficient heat insulating effect cannot be obtained because the heat insulating layer is not sufficiently formed.

From the viewpoint of shape retention during combustion, the weight ratio of the neutralized heat-expandable graphite to the phosphorus compound is preferably 0.01 to 5. Resin composition 5
Even if itself is flame retardant, if the shape retention is insufficient, the brittle residue collapses and there is a risk of causing the flame to penetrate, so the shape retention is required in the applied application. The mixing ratio of the neutralized heat-expandable graphite is selected depending on whether or not. More preferably, the range is 0.01-5.

The weight ratio of the polyhydric alcohol to the phosphorus compound [(polyhydric alcohol) / (phosphorus compound)] is from 0.05 to 20 from the viewpoint of exhibiting higher fire resistance and residue shape retention. It is preferred that When the weight ratio is less than 0.05, the foamed heat insulating layer becomes brittle and cannot be used, and when it exceeds 20, foam expansion does not occur and sufficient fire resistance cannot be obtained. More preferably,
It is 0.3-10, More preferably, it is 0.4-5.

The weight ratio of the above-mentioned metal carbonate to the above-mentioned phosphorus compound [(metal carbonate) / (phosphorus compound)] is from 0.01 to 50 from the viewpoint of exhibiting fire resistance and residue shape retention.
Is more preferable, more preferably 0.3 to 15, and still more preferably 0.5 to 7. The above weight ratio is 0.0
When it is less than 1, the foamed heat insulating layer becomes brittle. Since the phosphorus compound serves as a binder for the metal carbonate, if the above weight ratio exceeds 50, the phosphorus compound does not function as a binder, not only makes molding difficult, but also causes insufficient foaming expansion upon heating. Therefore, sufficient fire resistance cannot be obtained.

Although the mechanism of the fire resistance of the resin composition 4 is not necessarily clear, it is considered that it develops as follows. That is, the phosphorus compound is dehydrated and foamed by heating, and also acts as a carbonization catalyst. The polyhydric alcohol forms a carbonized layer by the catalytic action of the phosphorus compound, and forms a heat insulating layer having excellent shape retention. The metal carbonate acts as an aggregate and makes the carbonized layer more robust. The neutralized heat-expandable graphite expands at that time to form a heat-insulating layer, and acts more effectively to prevent heat transfer.

The refractory expansion sheet (a) of the present invention has a temperature of 25 ° C.
It is preferable that the bulk density at the initial stage is 0.8 to 2.0 g / cm3. The initial bulk density at 25C is 0.8-2.
When the content is within the range of 0 g / cm 3, physical properties such as heat insulation and fire resistance required for the fire-resistant expanded sheet (a) are not impaired, and excellent workability can be obtained.

The initial bulk density at 25 ° C. is 0.8 g /
If it is less than 3 cm3, a sufficient amount of an expanding agent, a carbonized layer and a non-combustible filler cannot be added to the resin composition, and the expansion ratio after heating and the amount of residues become insufficient. Cannot be formed. If the initial bulk density at 25 ° C. exceeds 2.0 g / cm 3, the weight of the resin composition becomes too large, so that the workability in attaching a large area resin composition and the like is reduced. More preferably, it is 1.0 to 1.8 g / cm3.

The fire resistant expansion sheet (a) has a bulk density of 0.05 to 0.5 g / c when heated at 500 ° C. for 1 hour.
Those having m3 are preferred. When the bulk density when heated at 500 ° C. for one hour is less than 0.05 g / cm 3,
Since there are too many gaps, it is impossible to form a refractory heat-insulating layer as a layer due to collapse during expansion, and 0.5 g / cm
If it exceeds 3, the expansion ratio becomes insufficient, fire resistance cannot be sufficiently exhibited, and a fire-resistant heat-insulating layer cannot be formed. More preferably, 0.1 to 0.3 g /
cm3.

The fire resistant expansion sheet (a) of the present invention has a thickness of 50 k.
The thermal conductivity after volume expansion for 30 minutes under the heating condition of W / cm 2 is preferably 0.01 to 0.3 kcal / m · h · ° C. The heat conductivity after the volume expansion for 30 minutes under the heating condition of 50 kW / cm 2 is 0.3 k
When cal / m · h · ° C. is exceeded, the heat insulation performance is insufficient, so that the fire resistance cannot be sufficiently exhibited.
Those having a temperature of less than 1 kcal / m · h · ° C. cannot be produced by a mixture of an organic substance and an inorganic substance.

The refractory expansion sheet (a) of the present invention preferably has a total heat absorption of 100 J / g or more when heated to 600 ° C. at a rate of 10 ° C./minute by a differential scanning calorimeter (DSC). . If it is at least 100 J / g, the temperature rise will be slow, and the heat insulation performance will be better.

In the present invention, it is preferable that the fire resistant expansion sheet has an adhesive property. Having tackiness means having a property that enables temporary fixing to a wall material, a metal plate (b) described below, or the like, and broadly having tackiness and / or adhesiveness. By making the fire-resistant expansion sheet sticky,
It can be easily bonded to a wall material, a metal plate (b), or the like, and the workability at the time of producing a fire-resistant structure wall is improved.

In order to impart tackiness to the fire resistant expansion sheet (a), for example, a tackifier may be added to the thermoplastic resin and / or rubber substance. The tackifier is not particularly limited, and includes, for example, tackifier resins, plasticizers, fats and oils, low-polymerized polymers, and the like. The tackifying resin is not particularly limited, and includes, for example, rosin, rosin derivative, dammar, copearl, cumarone, indene resin, polyterpene, non-reactive phenol resin, alkyd resin, petroleum hydrocarbon resin, xylene resin, epoxy resin, and the like. Is mentioned.

Although it is difficult for the plasticizer alone to impart tackiness to the fire-resistant expansion sheet, it is possible to further improve the tackiness when used in combination with the tackifying resin. The plasticizer is not particularly limited. For example, phthalate ester plasticizer, phosphate ester plasticizer, adipate ester plasticizer, sebacate ester plasticizer, ricinoleate ester plasticizer, polyester plasticizer Agents, epoxy plasticizers, chlorinated paraffins and the like. The above fats and oils have the same action as the above plasticizer, and can be used for the purpose of imparting plasticity and as a tackifier. The fats and oils are not particularly limited, and include, for example, animal fats and oils, vegetable fats and oils, mineral oils, silicone oils and the like.

The low polymer of the polymer can be used for the purpose of improving cold resistance and adjusting the flow in addition to imparting tackiness. The polymer low-polymer is not particularly limited. For example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), 1,2-butadiene rubber (1,2-B
R), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (IIR), ethylene-propylene rubber (EPM, E
PDM), chlorosulfonated polyethylene (CSM),
Low polymers such as acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluoro rubber (FKM, FZ), urethane rubber (U), etc. Can be

In the present invention, a flame retardant, an antioxidant, a metal harm inhibitor, an antistatic agent, and a stabilizer are added to the resin composition constituting the fire-resistant expansion sheet as long as the physical properties of the resin composition are not impaired. , A cross-linking agent, a lubricant, a softener, a pigment, a tackifying resin, and the like may be added.

The resin composition can be obtained by melt-kneading the above-mentioned components using a known kneading apparatus such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, and a two-roller. The resin composition can be formed into the fire-resistant expansion sheet by a conventionally known method such as press molding, extrusion molding, and calendar molding.

As the fire-resistant expansion sheet (a) of the present invention, a single layer of the fire-resistant expansion sheet formed as described above may be used, and a plurality of layers of the fire-resistant expansion sheet composed of the above resin compositions having different compositions are laminated. A multi-layered fire resistant expanded sheet may be used. Further, the fire-resistant expansion sheet (a) has a surface on which glass wool, rock wool, mineral wool, or a blanket thereof is used as long as the fire resistance is not impaired.
Woven fabric, non-woven fabric, paper or a composite thereof may be laminated, and when a metal plate described later is laminated on only one surface of the fire-resistant expansion sheet (a), the above-mentioned metal plate is laminated on the other surface. The refractory expansion sheet (a) may be laminated with a wire mesh or the like having a swelling allowance when the refractory expansion sheet (a) expands.

The above-mentioned metal plate (b) is laminated on the above-mentioned fire-resistant expansion sheet (a) for the purpose of preventing a fire-resistant panel and a fire-resistant structural wall using the same from penetrating a flame, and covers the back surface of the wall material. Is what is done. As shown in FIGS. 1 and 2, the metal plate (b) is laminated on at least one surface of the fire-resistant expansion sheet (a). The above metal plate (b)
It is not particularly limited, and examples thereof include an iron plate, a stainless steel plate, an aluminum plate, an aluminum / zinc alloy-plated steel plate, a surface-treated steel plate, a titanium plate, an enameled steel plate, a fluororesin-coated steel plate, a clad steel plate, and a copper plate. or,
The metal plate (b) may be used alone, or may be a composite metal plate in which metal plates made of different materials are laminated. The metal plate (b) may be laminated on the fire-resistant expansion sheet (a) in a flat state, but a shallow box whose periphery is slightly bent in the direction in which the fire-resistant expansion sheet (a) is laminated. The box-shaped metal plate (b) may be bent so that the opening of the metal plate (b) can be covered with the fire-resistant expansion sheet (a).

By making the peripheral edge of the metal plate (b) into a shallow box shape which is slightly bent so as to enclose the side edge of the fire-resistant expansion sheet (a), the fire-resistant panel of the present invention can be used as a wall material. When laminated on the back and used as a fire-resistant structure wall,
The flat hollow portion of the metal plate (b) bent into the box shape is secured as a swelling margin of the fire-resistant expansion sheet (a) expanded by heating, and a more reliable heat-insulating fire-resistant layer can be formed. .

The thickness of the metal plate (b) is 0.1-1.
5 mm. If the thickness of the metal plate (b) is less than 0.1 mm, it is not possible to prevent the occurrence of a flame path due to cracking of the exterior material in the event of a fire, and it is not possible to obtain sufficient fire resistance.
On the other hand, if it exceeds 1.5 mm, the above-mentioned fire-resistant expansion sheet (a)
In addition to inhibiting the expansion of the fireproof panel, not only the fireproof performance is reduced, but also the weight of the fireproof panel and the wall of the fireproof structure using the fireproof panel becomes difficult to handle, and the workability and the like are reduced.

The above-mentioned fire-resistant expansion sheet (a) and metal plate (b)
Means for laminating is not particularly limited, for example, may be bonded using cement or other adhesives,
They may be joined by nailing, screwing, or the like.

The above-mentioned fire-resistant expansion sheet (a) and metal plate (b)
As shown in FIG. 3, the fireproof panel on which
On the back surface of the wall material (c), the fire-resistant expansion sheet (a) may be laminated on the surface on which the metal plate (b) is not laminated, and as shown in FIG. The fire-resistant expansion sheet (a) is laminated on the surface on which the metal plate (b) is stacked, and the exposed surface of the fire-resistant expansion sheet (a) is finely divided over its entire surface as a swelling allowance of the fire-resistant expansion sheet (a). A metal lath, a wire mesh, or the like having a gap or a space gathered over the entire surface may be stretched so as to surround the side edge of the fire-resistant expansion sheet (a). Further, as shown in FIG. 5, a fire resistant expansion sheet (a) having a metal plate (b) laminated on both sides may be laminated on the back surface of the wall material (c). The means for coating the fireproof panel on the back surface of the wall material (c) is not particularly limited. For example, the refractory panel may be bonded using cement or another adhesive, and may be bonded by nailing, screwing, or the like. May be done.

The wall material (c) preferably has a thickness of 0.1 mm or more. If the thickness is less than 0.1 mm, the mechanical strength is insufficient, and the danger of flame penetration increases. Further, the thickness of the wall material (c) is determined according to the use of the fire-resistant structure wall. Therefore, the upper limit is not particularly limited. However, in the case of distributing as a panel in which the respective layers (a), (b), and (c) are laminated, the upper limit is preferably 50 mm or less in view of workability.

The fire-resistant panel of the present invention is laminated on the back surface of the wall material on the side directly exposed to the flame, but this does not exclude that the fire-resistant panel is used independently.

As described above, the fireproof panel of the present invention
It comprises a fire-resistant expansion sheet (a) and a metal plate (b). At the time of fire, the fire-resistant expansion sheet (a) is foamed and expanded on the back surface of the wall material to form a sufficient heat insulating layer. Therefore, the temperature rise of the building can be suppressed, and the flame can be reliably shut off without penetrating the refractory structure and causing fire.

In particular, in the present invention, the thickness of the refractory expansion sheet (a) and the thickness of the metal plate (b) are set to 0.3 to 5 respectively.
With the combination of 0.1 mm and 0.1 mm to 1.5 mm, it is possible to prevent the formation of a flame path due to cracking of the wall material at the time of a fire, etc., and to sufficiently expand the fire resistance performance by foaming and expanding the fire resistant expansion sheet (a). Further, the combination of the thicknesses described above makes it possible to produce the fire-resistant panel of the first aspect of the present invention and to coat it on the back surface of the wall material, thereby improving workability in producing the fire-resistant structure wall. Very easy,
Moreover, the workability of the obtained wall material is also extremely good.

According to a second aspect of the present invention, the relationship between the thickness (t) before heating and the thickness (t ′) after heating of the refractory expansion sheet (a) when heated to 300 ° C. is as follows: t '/ t =
The fireproof panel according to claim 1, which satisfies 1.1 to 20.

According to the second aspect of the present invention, as described above,
When heated to 0 ° C., the relationship between the thickness (t) of the refractory expansion sheet (a) before heating and the thickness (t ′) after heating is as follows:
Since t '/ t = 1.1 to 20 is satisfied, the fire-resistant expansion sheet (a) expands and foams so as to exhibit sufficient fire resistance performance even when sandwiched between the metal plates (b). At the same time, it is possible to maintain a shape in close contact with the back surface of the wall material, so that excellent fire resistance can be imparted to the wall material. Furthermore, since these excellent fire resistance performances are obtained by the combination of the thickness of the fire resistant expansion sheet (a) and the metal plate (b), the production of the fire resistant panel and the coating of the panel on the back surface of the wall material are performed. The workability during the production of fire-resistant structural walls is extremely easy, and the workability of the obtained wall material is extremely good. It is to let.

[0078]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Preparation of Fire-Resistant Expansion Sheet (a1)] 42 parts by weight of butyl rubber (trade name “Butyl 065” manufactured by Exxon Corp.), polybutene (trade name “100” manufactured by Idemitsu Petrochemical Co., Ltd.)
R ") 50 parts by weight, tackifier resin (manufactured by Exxon Corp., trade name" Escolets 5320 ") 8 parts by weight, thermally expandable graphite (UCAR Carbon Corp., trade name" GRAFGu ")
ard # 160 ", expansion temperature: 150 ° C) 30 parts by weight,
Ammonium polyphosphate (Hoechst, trade name "AP
422 "), 100 parts by weight, 75 parts by weight of aluminum hydroxide (manufactured by Showa Denko KK, trade name" H42M ") and calcium carbonate (Bikita Powder Co., Ltd., trade name" Whiteton BF-30 ")
0 ") 75 parts by weight were kneaded with a kneader, and a molding temperature of 13 was obtained using a twin-screw single-screw extruder equipped with a fishtail die.
Extrusion was performed at 0 ° C. to obtain a refractory expansion sheet (a1) having a thickness of 1.5 mm.

(Example 1) The fire resistant expansion sheet (a1)
As shown in FIG. 3, a fireproof panel of the type shown in FIG. 1 having a 0.3 mm thick zinc iron plate (b) laminated on one side of a ceramic siding (Nichiha Corporation, trade name "Moen") "Excellerd", 18 mm thick), on the opposite surface to the surface on which the zinc iron plate (b) is laminated, by sticking and laminating due to the adhesiveness of the fire resistant expansion sheet (a1). An 8 mm refractory wall was made.

(Example 2) The fire resistant expansion sheet (a1)
As shown in FIG. 4, a fire-resistant panel of the type shown in FIG. 1 in which a zinc iron plate (b) having a thickness of 0.3 mm was laminated on one side of a ceramic siding (manufactured by Nichiha Corporation, trade name "Moen Excellor") On the back surface of the zinc-iron plate (b), on the back surface of the "
A metal lath (Yamanaka Seisakusho Co., Ltd., trade name “YM type corrugated lath 1”)
No., a corrugated height of 10 mm) and a total thickness of 2 by laminating the refractory expansion sheet (a) so as to secure a swelling allowance.
A 9.8 mm refractory wall was made.

(Embodiment 3) The fire resistant expansion sheet (a1)
As shown in FIG. 5, a fireproof panel of the type shown in FIG. 2 in which a zinc iron plate (b) having a thickness of 0.25 mm was laminated on both sides of a ceramic siding (manufactured by Nichiha Corporation, trade name: "Moen excelad", thickness 18 mm) was laminated on the back surface to produce a refractory structure wall having a total thickness of 20 mm.

(Comparative Example 1) As shown in FIG. 6, a 0.3 mm thick zinc iron plate (b) was placed on the back surface of a ceramic siding (trade name "Moen Excelad", manufactured by Nichiha Corporation, thickness: 18 mm). They were laminated to produce a wall having a total thickness of 18.3 mm.

Comparative Example 2 The following fire-resistant expansion sheet (a
A wall having a total thickness of 19.8 mm was produced in the same manner as in Example 1 except that 2) was used.

[Preparation of Fire-Resistant Expansion Sheet (a2)] A fire-resistant expansion sheet was used except that 20 parts by weight of thermally expandable graphite (trade name “Frame Cut GREP-EG” manufactured by Tosoh Corporation) having an expansion start temperature of 200 ° C. was used. A fireproof expansion sheet (a2) having a thickness of 1.5 mm was obtained in the same manner as in the preparation of (a1).

The fire resistant walls of Examples 1-3 and Comparative Examples 1 and 2 were evaluated for fire resistance and shape retention by the following methods. The results are shown in Table 1.

(Evaluation Method) (1) Fire Resistance The fire resistance was evaluated in a refractory furnace as shown in FIG. In accordance with JIS A 1304, after the temperature in the furnace was raised to 925 ° C. in one hour, the back surface temperature of the ceramic siding was measured.

(2) Shape retention The evaluation sample after burning in the above fire resistance test did not collapse.
(Bad) was evaluated in two stages.

[0089]

[Table 1]

The fire-resistant structure walls of Examples 1 to 3 are manufactured using a fire-resistant panel made of a thin fire-resistant expansion sheet and a metal plate, so that the construction of the fire-resistant structure wall can be performed very smoothly. It could be implemented in a short construction period. The fire resistance performance of the constructed fire-resistant structure wall is clear from Table 1,
The temperature rise on the back side of the ceramic siding was also slight, and the shape retention after burning was extremely good so as to support the above fire resistance performance. On the other hand, in the wall of Comparative Example 1, the ceramic siding was cracked due to heating, and countless cracks were contained. Also, the temperature rise on the back surface of the ceramic siding was large as shown in Table 1, and it could not be used as a fire-resistant structure wall. In addition, the fireproof structure walls of Examples 1 to 3 are excellent in fireproof performance because the fireproof expansion sheet starts to expand at an earlier timing than in Comparative Example 2.

[0091]

The fireproof panel according to the first aspect of the present invention is
With the above-described structure, it is possible to prevent the formation of a flame path due to a crack in the fire-resistant structure wall at the time of a fire, etc., to reliably shut off the flame, and to increase the temperature of the building by foaming expansion of the fire-resistant expansion sheet (a). Can suppress the rise,
Further, the combination of the thicknesses described above makes it extremely easy to manufacture the fireproof panel of the present invention and to coat the backside of the wall material with the back surface of the wall material, thereby making workability of the fireproof structural wall extremely easy. The workability is also extremely good. In addition, since it contains thermally expandable graphite having a thermal expansion start temperature of 140 to 180 ° C, the timing of the expansion start is earlier than that of the conventional thermal expansion material, and the fire resistance is excellent.

According to the second aspect of the present invention, the thickness (t) before heating and the thickness (t ') after heating when the refractory expansion sheet (a) is heated to 300.degree. The relationship is t '
/T=1.1 to 20, so that the fire-resistant expansion sheet (a) expands and foams so as to exhibit sufficient fire resistance even when sandwiched between the metal plates (b). Since it can maintain a shape closely attached to the back surface of the wall material, excellent fire resistance can be imparted to the wall material. Furthermore, since these excellent fire resistance performances are obtained by the combination of the thickness of the fire resistant expansion sheet (a) and the metal plate (b), the production of the fire resistant panel and the coating of the panel on the back surface of the wall material are performed. The workability during the production of fire-resistant structural walls is extremely easy, and the workability of the obtained wall material is extremely good. It is to let.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a first embodiment of a fireproof panel of the present invention.

FIG. 2 is a schematic sectional view showing a second embodiment of the fireproof panel of the present invention.

FIG. 3 is a schematic sectional view showing an example of a fireproof structure wall using the fireproof panel of the present invention.

FIG. 4 is a schematic cross-sectional view showing another example of a fireproof structure wall using the fireproof panel of the present invention.

FIG. 5 is a schematic sectional view showing another example of a fireproof structure wall using the fireproof panel of the present invention.

FIG. 6 is a schematic sectional view showing a refractory structure wall of a comparative example.

FIG. 7 is a schematic cross-sectional view for explaining a method for evaluating fire resistance.

[Explanation of symbols]

 a: fire resistant expansion sheet b: metal plate c: wall material d: metal lath F: fire resistant furnace

Claims (3)

[Claims] 1. A fire-resistant expansion sheet (a) having a thickness of 0.3 to 5 mm and comprising a resin composition containing a neutralized heat-expandable graphite having an expansion start temperature of 140 to 180 ° C. And a metal plate (b) having a thickness of 0.1 to 1.5 mm. 2. When heated to 300 ° C., the relationship between the thickness (t) of the refractory expansion sheet (a) before heating and the thickness (t ′) after heating is t ′ / t = 1. 2. The fireproof panel according to claim 1, wherein 3. The fire-resistant expansion sheet (a) comprises a thermoplastic resin and / or a rubber substance, neutralized heat-expandable graphite, a phosphorus compound, and an inorganic filler. The total amount of the expandable graphite and the phosphorus compound is 20 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin and / or rubber substance, and the weight of the neutralized thermally expandable graphite and the phosphorus compound. The ratio [(neutralized heat-expandable graphite) / (phosphorus compound)] is 0.01 to 9, and the amount of the inorganic filler is 100 parts by weight of the thermoplastic resin and / or rubber substance. Weight ratio of the inorganic filler to the phosphorus compound [(inorganic filler)
/ (Phosphorus compound)] is a resin composition of 0.6 to 1.5, the fireproof panel according to claim 1 or 2.