JP2000006289A - Fireproof multilayer sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fireproof multilayer sheet comprising a resin composition containing a phosphorus compound, having an excellent form-retentability in a combustion residue, and a high fire proofness. SOLUTION: This refractory multilayer sheet is formed of a coating sheet layer (B) of 0.01-2 mm thickness laminated on at least one face of a heat expandable sheet layer (A) of 0.5-10 mm thickness. The thickness ratio of the heat expandable sheet layer (A) to the coating sheet layer (B) [layer (B)/layer (A)]=0.02-0.5. The heat expandable sheet layer (A) is formed of a resin composition containing a phosphorus compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fire-resistant multilayer sheet used for building materials such as ceiling materials, floor materials, partition walls, beams, columns and the like.

[0002]

2. Description of the Related Art Hitherto, fire resistance has been one of the important properties in the field of building materials. In recent years, a resin material has been used as a building material. With the expansion of use of the resin material, a resin material having more fire resistance has been required.

[0003] As a test method of fire resistance performance, for example, there is a method of measuring the temperature of the back surface when the front surface is heated to about 1000 ° C. In the case of building materials, the temperature of the back surface in this case is lower than 260 ° C. Is required.

For such fire resistance, not only the resin material itself is not easily burned, but also such a property that the flame is not transmitted to the back surface of the resin material is required. Resin components and organic components inherently have the property of burning or melting themselves, so how long does this state not occur, and how long do inorganic components fall off when containing inorganic components It is important to be able to hold without doing it.

As a method for exhibiting such properties in a resin material, for example, JP-A-6-25476 discloses a technique of adding a phosphorus compound and thermally expandable graphite to a polyolefin resin.

[0006] However, this technique can provide sufficient performance in terms of flame retardancy, but when a sheet-like molded product is used as a backing material for a wall or the like, only a brittle ash remains in a fire resistance test, and the combustion residue However, there were problems such as falling off and the back surface temperature rising to a reference value of 260 ° C. or more.

The above-mentioned sheet-like molded product is often used by bonding it to a building material such as a pillar or a wall material in order to prevent a temperature rise of a steel material or a wall material itself during combustion. For this reason, when used in a vertical part, it is necessary that the combustion residue that becomes the heat insulating layer from columns, wall materials, and the like be held without collapse during and after combustion. For this reason, the strength (shape retention) of the combustion residue is an important performance factor for a material having fire resistance.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fire-resistant multilayer sheet comprising a resin composition containing a phosphorus compound and having excellent fire-resisting shape retention of combustion residues.

[0009]

The refractory multilayer sheet of the present invention has a thermally expandable sheet layer (A) having a thickness of 0.5 to 10 mm.
A fire-resistant multilayer sheet in which a coating sheet layer (B) having a thickness of 0.01 to 2 mm is laminated on at least one side of the sheet, wherein the thickness ratio of the heat-expandable sheet layer (A) to the coating sheet layer (B) is [Layer (B) / Layer (A)] = 0.02 to 0.5,
The heat-expandable sheet layer (A) has a total amount of 20 to 200 parts by weight of the phosphorus compound and the neutralized heat-expandable graphite with respect to 100 parts by weight of the thermoplastic resin and / or the rubber substance. A resin composition in which the inorganic substance is 10 to 500 parts by weight, the metal carbonate is 10 to 500 parts by weight, and the weight ratio between the neutralized thermally expandable graphite and the phosphorus compound is 0.01 to 9 (I), wherein the coating sheet layer (B) is a thermoplastic resin and / or a rubber substance and 100 parts by weight of neutralized heat-expandable graphite is 10-80.
Parts by weight, and a total of 2 parts by weight of the metal carbonate and the hydrated inorganic substance.
It is characterized by being formed from the resin composition (II) containing up to 500 parts by weight.

[0010] The fire-resistant multilayer sheet of the present invention comprises a laminate in which a coating sheet layer (B) is laminated on at least one surface of a heat-expandable sheet layer (A). Further, the resin composition (I)
(A) composed of a resin and layer (B) composed of a resin composition (II)
Are laminated at a certain thickness ratio to form a layer (B)
Of the combustion residue enters the void portion of the combustion residue in the layer (A) to form a strong combustion residue.

The thickness of the heat-expandable sheet layer (A) is as follows:
0.5 to 10 mm. When the thickness is less than 0.5 mm, sufficient heat insulating properties are not exhibited even when expanded, and when the thickness exceeds 10 mm, the weight becomes heavy and the handleability deteriorates.

The thickness of the covering sheet layer (B) is 0.0
1 to 2 mm. When the thickness is less than 0.01 mm, the thickness of the combustion residue in the layer (B) is small, and the effect of reinforcing the combustion residue is not sufficiently exhibited. May reduce the performance.

The thickness ratio of the layer (A) to the layer (B) [layer (B) / layer (A)] is limited to 0.02 to 0.5.
If the thickness ratio [layer (B) / layer (A)] is less than 0.02, the effect of imparting heat insulation to layer (B) is not sufficient, and if it exceeds 0.5, the flame retardancy and shape retention of the multilayer sheet are obtained. In some cases, adversely affecting the fire resistance performance.

The heat-expandable sheet layer (A) comprises a resin composition (I) containing a thermoplastic resin and / or a rubber substance, a phosphorus compound, a neutralized heat-expandable graphite, a hydrated inorganic substance and a metal carbonate. ).

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

Of these, halogenated resins such as chloroprene-based resins and chlorinated butyl-based resins have high flame retardancy per se, and are crosslinked by a dehalogenation reaction by heat, and the strength of the residue after heating is high. Is preferred in that the Those exemplified as the resin component are very flexible and have rubber-like properties, so that the inorganic filler can be highly filled, and the obtained resin composition becomes flexible and flexible. . In order to obtain a more flexible and flexible resin composition, a non-vulcanized rubber or a polyethylene resin is preferably used. Non-vulcanized rubber and the like are also preferable in that the gas generated during combustion has low toxicity.

The above resin components may be used alone or in combination of two or more. In addition, the melt viscosity, flexibility,
For adjusting the adhesiveness or the like, a blend of two or more resins may be used.

The resin may be cross-linked or modified as long as the fire resistance is not impaired. When performing crosslinking or modification of the resin component, the resin component may be subjected to crosslinking or modification in advance, and crosslinking or modification is performed at the time of or after blending other components such as a phosphorus compound or an inorganic filler described below. May be applied.

The cross-linking method is not particularly limited, and includes a cross-linking method usually performed for the resin component, for example, a cross-linking method using various cross-linking agents and peroxides, and a cross-linking method by electron beam irradiation. .

The phosphorus compound is not particularly limited.
For example, red phosphorus; various phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and xylendiphenyl phosphate; phosphorus such as sodium phosphate, potassium phosphate, and magnesium phosphate Acid metal salts; ammonium polyphosphates; and compounds represented by the following general formula (1). 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.

[0021]

Embedded image

In the formula, R ¹ and R ³ represent a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms, or
Represents 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, or 6-1
6 represents an aryloxy group.

The flame retardant effect can be 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 limited, and 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 commercially available products, for example, “AP manufactured by Hoechst”
422 "," AP462 "," Terage C "manufactured by Chisso
70 "," Terage C80 "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 above phosphorus compounds may be used alone or in combination of two or more.

The neutralized heat-expandable graphite is obtained by neutralizing heat-expandable graphite which is a conventionally known substance. 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. Heat-expandable graphite.

The aliphatic lower amine is not particularly restricted but includes, for example, monomethylamine, dimethylamine,
Trimethylamine, ethylamine, propylamine, butylamine and the like. The alkali metal compound and the alkaline earth metal compound are not particularly limited,
For example, hydroxides, oxides, carbonates, sulfates, organic acid salts of potassium, sodium, calcium, barium, magnesium and the like can be mentioned. Commercial products of the neutralized heat-expandable graphite include, for example, “GR manufactured by Tosoh Corporation”
EP-EG "," GRAFGUARD "manufactured by UCAR, and the like.

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.

Examples of the hydrated inorganic substance include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and hydrotalcite. Examples of the metal carbonate include basic magnesium carbonate, calcium carbonate, and magnesium carbonate. , Zinc carbonate, strontium carbonate, barium carbonate and the like.

The above-mentioned hydrated inorganic substances such as magnesium hydroxide and aluminum hydroxide endothermic due to water generated by the dehydration reaction at the time of heating, so that the temperature rise is reduced and high heat resistance is obtained. Oxide remains as a residue, and it is particularly preferable in that it functions as an aggregate to improve the strength of the residue. Magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydrating effect is exhibited.
It is preferable to use them together because a more effective temperature rise suppression effect can be obtained.

The above metal carbonates such as calcium carbonate and zinc carbonate are considered to promote expansion by the reaction with the above phosphorus compound. Particularly, when ammonium polyphosphate is used as the phosphorus compound, a high expansion effect is obtained. Can be In addition, the metal carbonate functions as an effective aggregate, and forms a combustion residue having high shape retention after burning.

Among the above metal carbonates, further, alkali metal carbonates such as sodium carbonate; magnesium carbonate;
Preferred are alkaline earth metal carbonates such as calcium carbonate and strontium carbonate; and carbonates of Group IIb metals of the periodic table such as zinc carbonate.

In the resin composition (I), the compounding amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 500 parts by weight based on 100 parts by weight of the resin component. If the compounding amount is less than 20 parts by weight, the amount of the combustion residue after heating becomes insufficient, and if it exceeds 500 parts by weight, the mechanical properties are greatly reduced, and the product cannot be used.

The weight ratio of the neutralized heat-expandable graphite to the phosphorus compound (heat-expandable graphite / phosphorus compound) is 0.0
1 to 9. If the compounding ratio of the neutralized heat-expandable graphite increases, the expanded graphite during combustion scatters, and a sufficient expansion heat-insulating layer cannot be obtained.If the compounding ratio with the phosphorus compound increases, a sufficient expansion heat-insulating layer is obtained. Is not formed, and a sufficient heat insulating effect cannot be obtained.

In the resin composition (I), the amount of the water-containing inorganic substance is from 10 to 50 per 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the amount of combustion residues after heating becomes insufficient, and a fire-resistant heat-insulating layer cannot be formed. If the amount exceeds 500 parts by weight, good shape retention cannot be exhibited.

In the above resin composition (I), the compounding amount of the inorganic carbonate is from 10 to 50 per 100 parts by weight of the resin component.
0 parts by weight is preferred. If the amount is less than 10 parts by weight, the amount of combustion residues after heating becomes insufficient, so that a refractory heat-insulating layer cannot be formed. If the amount exceeds 500 parts by weight, good shape retention cannot be exhibited.

With respect to the above-mentioned thermoplastic resin and / or rubber substance, phosphorus compound, neutralized heat-expandable graphite, hydrated inorganic substance and metal carbonate, the same components will be used hereinafter.

The coating sheet layer (B) is a resin composition (II) containing a thermoplastic resin and / or a rubber substance, neutralized heat-expandable graphite, a hydrated inorganic substance, and a metal carbonate.
Formed from

In the resin composition (II), the amount of the neutralized heat-expandable graphite is from 10 to 80 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 10 parts by weight, the amount of combustion residues after heating will be insufficient, and if it exceeds 80 parts by weight, the mechanical properties will be greatly reduced, making it unusable for use.

In the resin composition (II), the total amount of the metal carbonate and the water-containing inorganic substance is 2 to 500 parts by weight based on 100 parts by weight of the resin component. If the amount is less than 2 parts by weight, the amount of combustion residues after heating becomes insufficient, and a fire-resistant heat-insulating layer cannot be formed. If the amount exceeds 500 parts by weight, good shape retention cannot be exhibited.

The above-mentioned covering sheet layer (B) may be formed of a resin composition (III) containing a thermoplastic resin and / or a rubber substance, neutralized heat-expandable graphite, and a hydrated inorganic substance. .

In the above resin composition (III), the blending amount of the neutralized heat-expandable graphite is as follows.
For the same reason as above, 10 parts by weight of resin
The amount is from 1 to 500 parts by weight based on 100 parts by weight of the resin component for the same reason as in the resin composition (II).

Further, the coating sheet layer (B) may be formed from a resin composition (IV) containing a thermoplastic resin and / or a rubber substance and a neutralized heat-expandable graphite. In the resin composition (IV), the blending amount of the neutralized heat-expandable graphite is 10 to 80 with respect to 100 parts by weight of the resin component for the same reason as in the resin composition (IV).
Parts by weight. Further, the cover sheet layer (B) may be formed from the resin composition (V).

The resin compositions (I), (II), (III),
(IV) and (V) include an inorganic filler, a thermally expandable mineral, a flame retardant, an antioxidant, and a metal damage inhibitor, which serve as an aggregate, as long as the physical properties of the resin composition are not impaired. , An antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, and the like may be added. In particular, layered minerals having a thermal expansion property other than the thermal expandable graphite, such as vermiculite, have different thermal expansion onset temperatures. Therefore, when they are used together, the fire resistance may be improved depending on the use site.

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

On one or both sides of the heat-expandable sheet layer (A) obtained from the resin composition (I), the coating obtained from the resin compositions (II), (III), (IV) and (V) is applied. By laminating the sheet layer (B), the fire-resistant multilayer sheet of the present invention can be obtained. As a method of laminating the heat-expandable sheet layer (A) and the covering sheet layer (B), a conventional laminating method such as a coextrusion method and a hot press method can be adopted.

The above-mentioned fire-resistant multilayer sheet comprises a heat-expandable sheet layer (A) and a coating sheet layer (B) containing no phosphorus compound.
Are stacked, and there is no particular limitation on the stacking order. Moreover, the structure which laminated | stacked the said covering sheet layer (B) on both sides of the said thermally expandable sheet layer (A) may be sufficient. In the early stage of the fire, the heat-expandable sheet layer (A) and the covering sheet layer (B) expand together to suppress a temperature rise. At the same time, the combustion residues of the layer (B) enter the gaps of the combustion residues of the layer (A), and form stronger residue hardness.

Since the coating sheet layer (B) does not contain a phosphorus compound, the shape retention of combustion residue itself is slightly inferior. If the fire further proceeds and expands sufficiently, the coating sheet layer (B) The combustion residue easily breaks down, and at this time, it enters the voids of the strong combustion residue formed by the thermally expandable sheet layer (A), and acts to make the combustion residue stronger. In addition, the combustion residue of the covering sheet layer (B) may collapse, but at this time, since the thermally expandable sheet layer (A) forms a strong combustion residue, the adiabatic expansion layer is not lost. Gives stable fire performance.

The refractory multilayer sheet of the present invention has a heat irradiation amount of 5
When completely burning under the condition of ₀ Kw / m ² , the relationship between the initial thickness (D ₀ ) and the thickness after burning (D ₁ ) is D ₁ / D ₀ =
It is preferably in the range of 1.1 to 20. D ₁ / D ₀
However, if it is less than 1.1, it does not exhibit sufficient heat insulating properties even when expanded by heating, and if it exceeds 20, the expansion ratio becomes too high and the strength of the combustion residue becomes insufficient.

The fire-resistant multilayer sheet of the present invention is used, for example, as a fire-resistant covering material for steel frames. When used as a fire-resistant covering material, it is preferable that after covering the above-mentioned fire-resistant multilayer sheet around a steel frame, a sheet made of a nonflammable material is further arranged outside the fire-resistant multilayer sheet.

The fire-resistant multilayer sheet receives heat in the event of a fire and expands to form a heat-insulating layer, and this heat-insulating layer prevents heat from being transmitted to the steel frame. Therefore, it is preferable that this heat insulating layer is formed without gaps all around the steel frame. Further, as the sheet made of the non-combustible material, a material that can be deformed to some extent following the heat insulating layer formed by the expansion of the fire-resistant multilayer sheet and can hold the shape of the heat insulating layer so as not to collapse is preferable.

Examples of the sheet made of the noncombustible material include:
It is not particularly limited as long as it has nonflammability, for example,
Metal plate materials such as steel plate, galvanized steel plate, stainless steel plate, aluminum / zinc alloy plate and aluminum plate; calcium silicate plate, fiber-mixed calcium silicate plate, calcium carbonate plate, gypsum board plate, reinforced gypsum plate, perlite cement plate, fiber Inorganic plates such as reinforced cement board, wood chip cement board, wood powder cement board, slag gypsum board and the like; sheet-like materials such as rock wool heat insulating board, ceramic wool blanket, alumina silica fiber felt, ceramic paper, aluminum hydroxide paper and the like. . The sheet made of the non-combustible material may be a sheet obtained by laminating a plurality of these sheets.

The sheet made of the noncombustible material is preferably a thin metal plate (foil). The thin metal plate absorbs the expansion without causing breakage or cutting by deforming or curving when the refractory sheet-like molded product expands. The thickness of the metal plate is preferably 0.1 to 1 mm. When the thickness is less than 0.1 mm, it does not function as a flameproofing material or a shape maintaining material. When the thickness exceeds 1 mm, it is difficult to secure an expansion allowance due to bending.

[0055]

Embodiments of the present invention will be described below. (Examples 1 to 4, Comparative Examples 1 to 3) Resins, hydrogenated petroleum resin, ammonium polyphosphate, neutralized heat-expandable graphite, aluminum hydroxide and the blending amounts shown in Tables 1 and 2 Calcium carbonate was supplied to separate twin-screw extruders, melted and kneaded, and then extruded from a co-extrusion mold to obtain a fire-resistant multilayer sheet having a thickness of 2 mm.

[0056]

[Table 1]

[0057]

[Table 2]

The components used in Tables 1 and 2 are as follows. -Metallocene PE (polyethylene): "EG8200" manufactured by Dow Chemical Company-Butyl rubber: "Butyl Rubber # 06" manufactured by Exxon Chemical Company
・ Polybutene: "Polybutene 100" manufactured by Idemitsu Petrochemical Co., Ltd.
R "・ Hydrogenated petroleum resin:" ESCOLETS 53 "manufactured by Tonex
20 "

-Ammonium polyphosphate: "AP422" manufactured by Clariant Co.-Neutralized heat-expandable graphite: "GREP" manufactured by Tosoh Corporation
-EG "・ Aluminum hydroxide: Showa Denko“ H-42M ”・ Calcium carbonate: Shiraishi calcium“ BF300 ”

The following items were evaluated for the performance of the fire-resistant multilayer sheet, and the results are shown in Table 3. (1) Expansion ratio With a refractory multilayer sheet (test piece) having a thickness of 10 cm × 10 cm × 2 mm placed horizontally, using a cone calorimeter (“CONE2A” manufactured by Atlas Co., Ltd.), 50 k
After being ignited by a spark and being completely burned under irradiation heat of W / m ² , the expansion ratio (D ₁
/ D ₀₎ was calculated. D ₁ : thickness of test piece of combustion residue, D ₀ : thickness of test piece before combustion test

(2) Breaking strength of combustion residue The combustion residue whose expansion ratio was evaluated in (1) was used as a test piece.
With the test piece placed horizontally, a load was applied to the test piece with a 0.25 cm diameter circular indenter at a speed of 0.1 cm / sec using a finger feeling tester (manufactured by Kato Tech Co., Ltd.). The maximum point that appears at the beginning of the load curve was taken as the breaking strength of the combustion residue. (If this maximum point is not observed, there will be no cohesive combustion residue,
When the combustion residue is set up vertically, it easily collapses and cannot protect the substrate to be insulated during combustion.) In this evaluation, if the maximum point is observed, the combustion residue can be held vertically, which is sufficient from the viewpoint of fire resistance. However, by making the combustion residue more robust, it becomes advantageous when a drop weight test or the like is required.

(3) Back surface temperature (° C.) After a fireproof multi-layer sheet of the same size is stuck on a SUS plate having a thickness of 10 cm × 10 cm × 0.3 mm and vertically installed, a cone calorimeter (“CONE” manufactured by Atlas Co., Ltd.) is used.
2A ”), the substrate was allowed to stand for 1 hour in a state where it was irradiated with 85 kW / m ² of irradiation heat, and the back surface temperature after 1 hour was measured.

[0063]

[Table 3]

From these examples, it can be seen that the fire-resistant multilayer sheet of the present invention can improve the hardness of the combustion residue without deteriorating the fire resistance during combustion.

[0065]

The fire-resistant multilayer sheet according to the present invention has the above-mentioned structure, and the heat-expandable sheet layer is formed from a resin composition containing a phosphorus compound. Excellent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 3/32 C08K 3/32 C08L 21/00 C08L 21/00 23/00 23/00 101/00 101 / 00

Claims (4)

[Claims] 1. A fire-resistant multilayer sheet comprising a heat-expandable sheet layer (A) having a thickness of 0.5 to 10 mm and a covering sheet layer (B) having a thickness of 0.01 to 2 mm laminated on at least one surface thereof. The heat-expandable sheet layer (A) and the covering sheet layer (B)
[Layer (B) / Layer (A)] = 0.02 to 0.5
Wherein the total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 20 with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance.
0 parts by weight, 10 to 500 parts by weight of hydrous inorganic material, and
The metal carbonate is 10 to 500 parts by weight, and the weight ratio between the neutralized heat-expandable graphite and the phosphorus compound is 0.01 to 9 parts by weight.
And the covering sheet layer (B) is formed from a thermoplastic resin and / or a rubber material 10.
0 parts by weight of neutralized heat-expandable graphite
A fire-resistant multilayer sheet comprising a resin composition (II) containing from 80 to 80 parts by weight, and from 2 to 500 parts by weight in total of a metal carbonate and a hydrated inorganic substance. 2. A fire-resistant multilayer sheet comprising a heat-expandable sheet layer (A) having a thickness of 0.5 to 10 mm and a covering sheet layer (B) having a thickness of 0.01 to 2 mm laminated on at least one surface thereof. The heat-expandable sheet layer (A) and the covering sheet layer (B)
[Layer (B) / Layer (A)] = 0.02 to 0.5
Wherein the total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 20 with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance.
0 parts by weight, 10 to 500 parts by weight of hydrous inorganic material, and
The metal carbonate is 10 to 500 parts by weight, and the weight ratio between the neutralized heat-expandable graphite and the phosphorus compound is 0.01 to 9 parts by weight.
And the covering sheet layer (B) is formed from a thermoplastic resin and / or a rubber material 10.
0 parts by weight of neutralized heat-expandable graphite
A fire-resistant multilayer sheet characterized by being formed from a resin composition (III) comprising from 80 to 80 parts by weight and a hydrous inorganic substance from 1 to 500 parts by weight. 3. A fire-resistant multilayer sheet comprising a heat-expandable sheet layer (A) having a thickness of 0.5 to 10 mm and a covering sheet layer (B) having a thickness of 0.01 to 2 mm laminated on at least one surface thereof. The heat-expandable sheet layer (A) and the covering sheet layer (B)
[Layer (B) / Layer (A)] = 0.02 to 0.5
Wherein the total amount of the phosphorus compound and the neutralized thermally expandable graphite is 20 to 20 with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance.
0 parts by weight, 10 to 500 parts by weight of hydrous inorganic material, and
The metal carbonate is 10 to 500 parts by weight, and the weight ratio between the neutralized heat-expandable graphite and the phosphorus compound is 0.01 to 9 parts by weight.
And the covering sheet layer (B) is formed from a thermoplastic resin and / or a rubber material 10.
0 parts by weight, neutralized heat-expandable graphite 10
A fire-resistant multilayer sheet formed of a resin composition (IV) consisting of 80 parts by weight. 4. A fire-resistant multilayer sheet comprising a heat-expandable sheet layer (A) having a thickness of 0.5 to 10 mm and a covering sheet layer (B) having a thickness of 0.01 to 2 mm laminated on at least one surface thereof. The heat-expandable sheet layer (A) and the covering sheet layer (B)
[Layer (B) / Layer (A)] = 0.02 to 0.5
Wherein the total amount of the phosphorus compound and the neutralized heat-expandable graphite is 20 to 20 with respect to 100 parts by weight of the thermoplastic resin and / or rubber substance.
0 parts by weight, 10 to 500 parts by weight of hydrous inorganic material, and
The metal carbonate is 10 to 500 parts by weight, and the weight ratio between the neutralized heat-expandable graphite and the phosphorus compound is 0.01 to 9 parts by weight.
And the covering sheet layer (B) is formed from a thermoplastic resin and / or a rubber material 10.
0 parts by weight, neutralized heat-expandable graphite 10
A fire-resistant multilayer sheet comprising a resin composition (V) comprising 80 parts by weight and 2 to 500 parts by weight of a metal carbonate.