JPH11333989A - Fire resistant multi-layered sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a fire resistant and heat insulating layer excellent in fire resistance performance by laminating each layer having a specified thickness and a specified range of resin composition. SOLUTION: A fire resistant multi-layered sheet is composed by laminating a layer B having 0.01-2 mm thickness on at least one side of a layer A having 0.5-10 mm thickness. The layer A is composed of a resin composition containing 100 pts.wt. of a thermoplastic resin and/or rubber substance, a total amount of 20-500 pts.wt. of a phosphorus compound and neutralized thermal expansion graphite, 10-500 pts.wt. of a water-containing inorganic substance and 10-500 pts.wt. of a metallic carbonate, wherein a weight ratio of the neutralized thermal expansion graphite and the phosphorus compound is 0.01-9. The layer B is composed of a resin composition containing 100 pts.wt. of a thermoplastic resin and/or rubber substance, 20-300 pts.wt. of a phosphorus compound, 10-470 pts.wt. of a water-containing inorganic substance and 10-470 pts.wt. of a metallic carbonate, wherein the total amount of the phosphorus compound, the water-containing inorganic substance and the metallic carbonate is 40-500 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fire-resistant multilayer sheet used for building materials such as ceiling materials, floor materials, and partition walls.

[0002]

2. Description of the Related Art Building materials are required to have fire resistance, that is, a property that is not easily flammable 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, for example, there is a method of measuring the back surface temperature by heating from the front surface. In building materials, when the front surface is heated to about 1000 ° C., the back surface temperature is required to be lower than 260 ° C. Have been.

[0003] As a building material having such excellent fire resistance, fire-resistant walls made of materials such as gypsum, perlite, and ALC are widely used. However, in order for these materials to exhibit sufficient fire resistance, it is necessary to increase the thickness, and when the thickness is increased, 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, the main purpose of this technology is to prevent a flame from going to the back surface by preventing a gap from being generated in the joint portion due to shrinkage of the fire-resistant wall,
There was a problem that it was 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] In order to improve workability, a building panel in which a plate made of a nonflammable inorganic material or resin is sandwiched between two metal plates has been developed. The temperature was higher than the reference value of 260 ° C., which was insufficient in terms of fire resistance.

Further, a fire-resistant resin sheet in which a large amount of a heat-expandable inorganic material is mixed in a resin has been studied as a building material. Such a resin sheet expands by heating to form a fire-resistant heat-insulating layer (combustion residue), and exhibits fire-resistant performance. Usually, the resin sheet is often attached to a building material such as a pillar or a wall material in order to prevent a temperature rise of the steel material or the wall material itself during combustion. For this reason, when used in a vertical part, both at the time of combustion and after combustion, combustion residues that become a fire-resistant insulation layer from columns, wall materials, etc. do not collapse,
It needs to be held. For this reason, the strength (shape retention) of the combustion residue is an important performance factor of a material exhibiting fire resistance.

In order to impart shape retention to the combustion residue, it is conceivable to reinforce it with a shape retaining material such as a wire mesh or a stainless steel plate. However, the shape retaining material hinders the expansion of the resin sheet during combustion. Instead, in order to form a sufficient fire-resistant heat-insulating layer, it is important to balance the expansion force of the resin sheet during combustion with the rigidity of the shape-retaining material.

However, the balance between the expansion force of the resin sheet and the rigidity of the shape-retaining material is determined by actually conducting a fire resistance test and determining that the foamed and expanded combustion residue has a predetermined fire insulation and strength. It is necessary to judge whether or not it takes time, which is a problem. Although a ceramic blanket may be used as a flexible shape-retaining material, it is difficult to set the thickness to 2 mm or less, and metal fittings such as pins are required for installation. There is a problem that the expansion of the sheet is hindered, and the temperature of this portion is locally increased.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a refractory heat-insulating layer (combustion residue) which is foamed and expanded at the time of combustion and has excellent refractory performance.
It is another object of the present invention to provide a fire-resistant multilayer sheet in which the obtained heat-insulating layer has excellent shape retention.

[0011]

According to a first aspect of the present invention, there is provided a fire-resistant multilayer sheet having a thickness of 0.5 to 10 mm on at least one surface of an A layer having a thickness of 0 to 10 mm. A fire-resistant multilayer sheet in which a B layer having a thickness of 0.01 to 2 mm is laminated, wherein the A layer comprises 100 parts by weight of a thermoplastic resin and / or a rubber substance, a phosphorus compound and neutralized heat-expandable graphite. 20 to 500 parts by weight in total, 10 to 500 parts by weight of hydrated inorganic substance, and 10 to 500 parts of metal carbonate
Parts by weight, and is formed from the resin composition (I) in which the weight ratio between the neutralized thermally expandable graphite and the phosphorus compound is 0.01 to 9, and the B layer comprises a thermoplastic resin and / 100 parts by weight of a rubber substance, 20 to 300 parts by weight of a phosphorus compound, 10 to 470 parts by weight of a hydrated inorganic substance, and 10 to 470 parts by weight of a metal carbonate, and a mixture of a phosphorus compound, a hydrated inorganic substance and a metal carbonate. It is characterized by being formed from the resin composition (II) having a total amount of 40 to 500 parts by weight.

The layer A is made of a resin composition (I) containing a thermoplastic resin and / or a rubber component, a phosphorus compound, neutralized thermally expandable graphite, a hydrated inorganic substance and a metal carbonate. It is formed.

The B layer is formed from a resin composition (II) containing a resin component comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound, a hydrated inorganic substance and a metal carbonate.

The above resin component is not particularly limited. For example, polyolefin resins such as polypropylene resin and polyethylene resin, 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, etc. No.

Of these, halogenated resins such as chloroprene-based resins and chlorinated butyl-based resins have high flame retardancy by themselves, and further, cross-linking occurs due to dehalogenation reaction by heat, resulting in residue after heating. Is preferred in that the strength of the resin is improved. 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.

The above resin components may be used alone or in combination of two or more. For adjusting the melt viscosity, flexibility, adhesiveness, etc. of the resin components, a blend of two or more resin components may be used as the base resin.

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 generally performed for the resin component, for example, a cross-linking method using various cross-linking agents, peroxides and the like, a cross-linking method by electron beam irradiation, and the like. .

It is preferable that the melting and softening temperatures of the resin component are lower than the expansion start temperature of the neutralized heat-expandable graphite described later.

The phosphorus compound is not particularly limited.
For example, red phosphorus; various phosphates such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 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 "," Sumisafe P "manufactured by Sumitomo Chemical Co., Ltd.," Terage C60 "," Terage C70 "," Terage C80 "and the like manufactured by Chisso.

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 "," GRAF "manufactured by UCAR Carbon
GUARD # 160 "," GRAFGUARD # 22
0 "and the like.

The particle size of the neutralized heat-expandable graphite is preferably 20 to 200 mesh. If the particle size is smaller than 200 mesh, the degree of expansion of graphite is small,
When a predetermined refractory heat-insulating layer cannot be obtained and the particle size is larger than 20 mesh, there is an advantage that the degree of expansion of graphite is large, but when kneaded with a resin component, dispersibility becomes poor, and deterioration of physical properties is inevitable. .

Examples of the above-mentioned hydrated inorganic substance include calcium hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite and the like. These may be used alone or in combination of two or more.

The aluminum hydroxide has a particle size of 1
μm “H-42M” (manufactured by Showa Denko KK), particle size 18 μm
"H-31" (manufactured by Showa Denko KK).

Examples of the above-mentioned metal carbonate include sodium carbonate, basic magnesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, zinc carbonate and the like. These may be used alone or in combination of two or more.

Examples of commercially available calcium carbonate include "Whiteton SB Red" having a particle size of 1.8 μm (manufactured by Shiraishi Calcium Co., Ltd.) and "BF300" having a particle size of 8 μm (manufactured by Shiraishi Calcium Co., Ltd.). .

The above-mentioned hydrated inorganic substance is endothermic due to water generated by the dehydration reaction at the time of heating, the temperature rise is reduced and high heat resistance is obtained, and an oxide remains as a heating residue. It is particularly preferable in that it works as an aggregate to improve residue strength. Magnesium hydroxide and aluminum hydroxide have different temperature ranges in which the dehydration effect is exhibited, so when used together, the temperature range in which the dehydration effect is exhibited expands, and a more effective temperature rise suppression effect is obtained. preferable.

When ammonium polyphosphate is used as the phosphorus compound, the metal carbonate promotes expansion by reaction with ammonium polyphosphate. In addition, it acts as an effective aggregate and forms a combustion residue having high shape retention after burning.

Since the above-mentioned hydrated inorganic substances and metal carbonates act as aggregates, they are considered to contribute to the improvement of the strength of combustion residues and the increase of heat capacity. In the present invention, an inorganic filler may be added in addition to the hydrated inorganic substance and the metal carbonate.

The particle diameter of the hydrated inorganic substance and the metal carbonate is preferably 0.5 to 100 μm, more preferably 1 to 50 μm. Further, it is more preferable to use a combination of a large particle size and a small particle size, and by such a combination, it is possible to achieve high filling while maintaining the mechanical performance of the sheet-like molded body. Becomes

When the amount of the hydrated inorganic substance and the metal carbonate is small, it is preferable that the particle diameter is small because the dispersibility greatly affects the performance. However, when it is less than 0.5 μm, secondary aggregation occurs, and the dispersibility is low. Gets worse. When the addition amount of the hydrated inorganic substance and the metal carbonate is large, the viscosity of the resin composition increases and the moldability decreases as the high filling proceeds, but the viscosity of the resin composition decreases by increasing the particle size. From the viewpoint that the particles can be used, those having a large particle diameter are preferable in the above range. On the other hand, when the particle size exceeds 100 μm, the surface properties of the molded article and the mechanical properties of the resin composition decrease.

The particle diameter of the hydrated inorganic substance and the metal carbonate is as follows:
When the particle size is small, the bulk becomes large and it is difficult to achieve high filling. Therefore, a large particle size is preferable for high filling in order to enhance the dewatering effect. Specifically, when the particle size is 18 μm,
It is known that the filling limit is improved by about 1.5 times as compared with the particle diameter of 1.5 μm. Further, by combining a material having a large particle size and a material having a small particle size, higher filling can be achieved.

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 physical properties such as elongation of the resin composition (I) are reduced, and the moldability is significantly reduced. A molded article having a good surface cannot be obtained.

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 heat-expandable graphite subjected to the neutralization treatment increases, the expanded graphite at the time of combustion scatters, and a sufficient refractory heat insulating layer is not formed.If the compounding ratio with the phosphorus compound increases, a sufficient refractory heat insulating layer is obtained. Is not formed, so that sufficient fire insulation cannot be obtained.

In the above resin composition (I), the amount of the water-containing inorganic substance is from 10 to 50 parts by weight per 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the heat absorbing effect due to dehydration during combustion is insufficient, so that the heat insulating effect during combustion becomes insufficient. If the amount exceeds 500 parts by weight, the elongation characteristics of the resin composition (I) are significantly reduced. .

In the resin composition (I), the amount of the metal carbonate is 10 to 50 parts by weight based on 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the strength of the combustion residue after heating becomes insufficient because the amount of aggregate is insufficient, and if it exceeds 500 parts by weight, the elongation characteristics of the resin composition (I) are remarkably deteriorated.

In the above resin composition (II), a resin component comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound,
As the hydrated inorganic substance and the metal carbonate, the same components as those of the resin composition (I) are used.

In the resin composition (II), the amount of the phosphorus compound is 20 to 30 parts by weight based on 100 parts by weight of the resin component.
0 parts by weight. If the compounding amount is less than 20 parts by weight, the amount of combustion residues after combustion becomes insufficient, and if it exceeds 300 parts by weight, the properties such as elongation of the resin composition (II) are reduced, and the moldability is significantly reduced. A molded article having a good surface cannot be obtained.

In the above resin composition (II), the compounding amount of the hydrated inorganic substance is 10 to 47 parts by weight per 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the heat absorbing effect due to dehydration during combustion is insufficient, so that the heat insulating effect during combustion is insufficient. If the amount exceeds 470 parts by weight, the physical properties such as elongation of the resin composition (II) are reduced. Since the moldability is greatly reduced, a molded article having a good surface cannot be obtained.

In the resin composition (II), the compounding amount of the metal carbonate is 10 to 47 parts by weight per 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the strength of the combustion residue after heating becomes insufficient, and if it exceeds 470 parts by weight, the elongation characteristics of the resin composition (II) are remarkably deteriorated.

In the resin composition (II), the total amount of the phosphorus compound, the hydrated inorganic substance and the metal carbonate is 40 to 500 parts by weight based on 100 parts by weight of the resin component. If the compounding amount is less than 40 parts by weight, due to insufficient combustion residue and insufficient combustion residue strength, sufficient heat insulating performance cannot be exhibited and also a role as a shape retaining material cannot be exhibited.
If the amount exceeds 500 parts by weight, the elongation characteristics of the resin composition (II) are remarkably deteriorated, so that it is difficult to form the sheet into a flexible sheet, or the workability is deteriorated due to poor followability to the steel frame to be coated. I do.

The resin composition (I) or the resin composition (I
I) can be obtained by supplying each component constituting the resin composition to a conventionally known kneading device such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneader mixer, or a two-roll, and melt-kneading the components. it can. The obtained resin composition,
For example, the sheet for the layer A or the layer B can be obtained by forming the sheet into a sheet by a conventionally known forming method such as extrusion molding or calendering.

By laminating the sheet for layer B on one or both sides of the sheet for layer A, the fire-resistant multilayer sheet of the present invention can be obtained. To obtain a fire resistant multilayer sheet,
For example, there is a method in which a sheet for layer A and a sheet for layer B are overlapped and laminated by press molding. Further, the resin composition (I) and the resin composition (II) are supplied to separate extruders, respectively, and co-extruded to form the layer A and the layer B.
A fire-resistant multilayer sheet in which layers are laminated may be obtained.

In the fire-resistant multilayer sheet of the first invention, A
The thickness of the layer is 0.5 to 10 mm, and the thickness of the B layer is
It is 0.01 to 2 mm. When the thickness of the A layer is less than 0.5 mm, a refractory heat insulating layer having a sufficient thickness is not formed after combustion,
If it exceeds 10 mm, the workability deteriorates. Further, if the thickness of the B layer is less than 0.01 mm, the thickness of the carbonized layer formed after combustion is insufficient, so that sufficient shape retention cannot be exhibited and 2 mm
If it exceeds, the workability will decrease.

Next, the second aspect of the invention will be described. The fire-resistant multilayer sheet of the second invention is a fire-resistant multilayer sheet in which a C layer having a thickness of 0.01 to 2 mm is laminated on at least one surface of an A layer having a thickness of 0.5 to 10 mm, The layer is composed of 100 parts by weight of a thermoplastic resin and / or a rubber substance, 20 to 500 parts by weight in total of a phosphorus compound and neutralized heat-expandable graphite, 10 to 500 parts by weight of a hydrated inorganic substance, and metal carbonate. The C layer is formed from the resin composition (I) containing 10 to 500 parts by weight of a salt and having a weight ratio of the neutralized thermally expandable graphite to the phosphorus compound of 0.01 to 9; 100 parts by weight of thermoplastic resin and / or rubber substance, phosphorus compound 20
Formed from the resin composition (III), which comprises from 300 to 300 parts by weight, and from 10 to 480 parts by weight of the metal carbonate, and the total amount of the phosphorus compound and the metal carbonate is from 30 to 500 parts by weight. It is characterized by the following.

In the second invention, the A layer is the A layer of the first invention.
The same thing as a layer is used.

In the second invention, the C layer is formed from a resin composition (III) containing a resin component comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound and a metal carbonate.

The same components as those of the first invention are used as the resin component comprising the thermoplastic resin and / or the rubber substance, the phosphorus compound and the metal carbonate.

In the above resin composition (III), the amount of the phosphorus compound is from 20 to 30 parts by weight per 100 parts by weight of the resin component.
0 parts by weight. If the compounding amount is less than 20 parts by weight, the amount of combustion residue after heating becomes insufficient, and if it exceeds 300 parts by weight, the physical properties such as elongation of the resin composition (III) are reduced, and the moldability is significantly reduced. A molded article having a good surface cannot be obtained.

In the above resin composition (III), the compounding amount of the metal carbonate is from 10 to 48 parts per 100 parts by weight of the resin component.
0 parts by weight. If the amount is less than 10 parts by weight, the strength of the combustion residue after heating becomes insufficient, and if it exceeds 480 parts by weight, the elongation characteristics of the resin composition (III) are remarkably deteriorated.

In the above resin composition (III), the total amount of the phosphorus compound and the metal carbonate is 10%.
It is 30 to 500 parts by weight with respect to 0 parts by weight. When the compounding amount is less than 30 parts by weight, a sufficient heat insulating effect is not exerted and the role as a shape retaining material cannot be exhibited due to a shortage of the combustion residue and insufficient combustion residue strength. Since the elongation characteristics of the composition (III) are significantly reduced, it is difficult to form a sheet having good surface properties.

The resin composition (III) can be obtained by melt-mixing the components by the same method as in the first invention. Using this resin composition (III), a C layer is obtained by the same method as in the first invention, and the A layer and the C layer are laminated by the same method as in the first invention, thereby obtaining the second invention. A fire-resistant multilayer sheet can be obtained. Further, similarly to the first invention, a fire-resistant multilayer sheet in which the A layer and the C layer are laminated may be obtained by co-extrusion of the resin compositions (I) and (III).

In the fire-resistant multilayer sheet of the second invention, the thickness of the layer A is 0.5 to 10 mm and the thickness of the layer B is 0.01 to 2 m for the same reason as the fire-resistant multilayer sheet of the first invention.
m.

The above resin compositions (I), (II) and (III)
In the range that does not impair the physical properties of the resin composition, a flame retardant,
An antioxidant, a metal harm inhibitor, an antistatic agent, a stabilizer, a crosslinking agent, a lubricant, a softener, a pigment, and the like may be added. Also,
A tackifier may be added to impart tack to the fire-resistant multilayer sheet.

[0062]

According to the first aspect of the present invention, there is provided a fire-resistant multilayer sheet comprising a resin component comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound, a neutralized heat-expandable graphite, a metal carbonate, and a hydrated inorganic material. On at least one surface of the layer A formed from the product (I), a resin composition containing a thermoplastic resin and / or a rubber material, a phosphorus compound, a metal carbonate, and a hydrated inorganic material are formed. The layer B is laminated, the layer A expands during combustion to form a refractory and heat-insulating layer composed of combustion residues, and the layer B forms a carbonized layer by combustion. Since the carbonized layer formed by burning the layer B does not contain the neutralized heat-expandable graphite, the expansion ratio is small and the heat insulating performance is inferior to the layer A, but the rigidity is excellent. It functions as a material and exhibits excellent fire resistance performance in two layers.

The fire-resistant multi-layer sheet of the second invention comprises a resin component comprising a thermoplastic resin and / or a rubber substance, a phosphorus compound,
At least one surface of the layer A formed from the resin composition (I) containing the neutralized heat-expandable graphite, the metal carbonate, and the hydrated inorganic material has a resin content of a thermoplastic resin and / or a rubber substance, A layer C formed from a resin composition (III) containing a compound and a metal carbonate is laminated, and the layer A expands during combustion to form a refractory and heat-insulating layer composed of combustion residues. A carbonized layer is formed by combustion. The carbonized layer formed by burning the layer C does not contain the neutralized heat-expandable graphite, and therefore has a small expansion ratio and is inferior in heat insulation performance to the layer A but has excellent rigidity. It functions as a material and exhibits excellent fire resistance performance in two layers. Further, the carbonized layer of the C layer does not contain a water-containing inorganic substance and thus is inferior in heat-absorbing effect as compared with the first invention, but has more excellent rigidity and thus functions as a shape-retaining material of the fire-resistant heat-insulating layer.

The fire-resistant multilayer sheet of the present invention is used as a fire-resistant covering material such as a steel frame. When used as a fire-resistant covering material, it is preferable to arrange the above-described fire-resistant multilayer sheet around a steel frame and further arrange a sheet made of a non-combustible material on the outside thereof. Regarding the placement method, it may be done sequentially from the inside, for steel frame,
A fire-resistant multi-layer sheet and a sheet made of a non-combustible material which have been laminated in advance may be arranged.

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

The sheet made of the above noncombustible material includes
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, aluminum plate, etc .; 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 flour cement board, slag gypsum board, etc .; sheet-like materials such as rock wool insulation board, ceramic wool blanket, alumina silica fiber felt, ceramic paper, aluminum hydroxide paper . 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 due to deformation or bending when the refractory sheet-like molded product or sheet laminate expands. The thickness of the metal plate is 0.1
１1 mm is preferred. 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.

The layer A in the above fire-resistant multilayer sheet has a relationship between the initial thickness (D ₀ ) and the thickness after burning (D ₁ ) when completely burned under the condition of a heat irradiation of 50 kW / cm ^2. ,
It is preferable that D ₁ / D ₀ = 1.1 to 20. When D ₁ / D ₀ is less than 1.1, sufficient heat insulating properties are not exhibited even when expanded by heating, and when it exceeds 20, the expansion ratio becomes too high and the strength of the combustion residue becomes insufficient.

[0069]

Embodiments of the present invention will be described below. (Examples 1 to 4, Comparative Examples 1 and 2) Resins, hydrogenated petroleum resin, ammonium polyphosphate,
The neutralized heat-expandable graphite, aluminum hydroxide, and calcium carbonate are supplied to a twin-screw extruder, melt-kneaded, extruded from a T-die, and formed into a sheet for an A layer having a thickness shown in Table 1, A sheet for layer B and a sheet for layer C were obtained. A above
Table 2 shows the sheet for layer and the sheet for layer B or the sheet for layer C.
And press-molded to obtain a fire-resistant multilayer sheet. In Comparative Example 1, a lath wire mesh was used to reinforce the B / C layer, and in Comparative Example 2, an iron plate was used to reinforce the B / C layer.

[0070]

[Table 1]

The components used in Table 1 are as follows. -Butyl rubber: "Butyl rubber # 06" manufactured by Exxon Chemical
・ Polybutene: "Polybutene 100" manufactured by Idemitsu Petrochemical Co., Ltd.
R "Metallocene PE:" EG8200 "manufactured by Dow Chemical Co., Ltd.-Hydrogenated petroleum resin:" ESCOLETS 53 "manufactured by Tonex
Ammonium polyphosphate: “AP4” manufactured by Clariant
22 ”・ Neutralized heat-expandable graphite:“ GREG ”manufactured by Tosoh Corporation
-EG "・ Aluminum hydroxide: Showa Denko“ H-42M ”・ Calcium carbonate: Shiraishi calcium“ BF300 ”

The following items were evaluated for the fire-resistant multilayer sheet and the sheet for each layer, and the results are shown in Table 2.

(1) Expansion Ratio 50 kW using a cone calorimeter (“CONS2A” manufactured by Atlas) with a fire-resistant multilayer sheet (test piece) having a thickness of 10 cm × 10 cm × 3 mm placed horizontally.
/ M ² , irradiated with a spark, ignited by a spark and completely burned, and then cooled to room temperature. The thickness of the test piece after cooling was measured, and the expansion ratio (thickness after heating / thickness before heating) was calculated from the thickness ratio before and after heating.

(2) Fireproof performance After a fireproof multilayer sheet (test piece) was placed vertically on the back of a stainless steel plate of 10 cm × 10 cm × 0.5 mm, and placed vertically, a cone calorimeter (“CONE2A” manufactured by Atlas Co., Ltd.) was used. ), 50k on the stainless steel plate side
The specimen was burned while being irradiated with an irradiation calorie of W / m ² , and the back surface temperature of the test piece after 1 hour was measured.

(3) Flameproofing performance of layer B or C When the fire resistance of (2) was measured, the sagging of the test piece from the start of combustion was visually observed from the side, and no sagging was observed. , And those with confirmed dripping were judged as x.

(4) Partial Inhibition of Expansion of Layer B or C When measuring the fire resistance of (2), a thermoviewer (manufactured by JEOL Datum) was placed on the back side to measure the temperature unevenness during combustion. 5cm × 5c out of 10cm × 10cm specimen
Within the area of m, those having a temperature distribution within ± 10 ° C. were indicated by ○, and those having a temperature distribution exceeding ± 10 ° C. were indicated by x.

(5) Inhibition of expansion of B layer or C layer The expansion ratio of (1) was measured for the case of the A layer alone and the case of the laminate of the A layer and the B or C layer. When the rate of change of the expansion ratio represented by the following formula was less than 5%,
Those that were 5% or more were indicated by x. Change rate of expansion ratio = [(A layer + B layer or C layer) / A layer]
× 100

[0078]

[Table 2]

[0079]

The fire-resistant multi-layer sheet of the present invention is obtained by laminating the B layer or the C layer on at least one side of the A layer.
The layer foams and expands during combustion to form a refractory heat insulating layer (combustion residue) having excellent fire resistance, and the layer B or C forms a carbonized layer during combustion to exhibit rigidity as a shape-retaining material.
Form a fire-resistant heat-insulating layer with excellent shape retention.

Claims (2)

[Claims] 1. A fire-resistant multilayer sheet in which a layer B having a thickness of 0.01 to 2 mm is laminated on at least one surface of a layer A having a thickness of 0.5 to 10 mm, wherein the layer A is formed of a thermoplastic resin. 100 to 100 parts by weight of resin and / or rubber substance, 20 to 500 in total amount of phosphorus compound and neutralized heat-expandable graphite
Parts by weight, 10 to 500 parts by weight of a hydrated inorganic substance, and 10 to 500 parts by weight of a metal carbonate, and the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound is 0.01 to 500 parts by weight.
9, the B layer is formed of 100 parts by weight of a thermoplastic resin and / or a rubber substance, 20 to 300 parts by weight of a phosphorus compound, 10 to 470 parts by weight of a hydrated inorganic substance, and 10 parts by weight of a metal carbonate. 470 parts by weight, and
When the total amount of the phosphorus compound, the hydrated inorganic substance and the metal carbonate is 40
A fire-resistant multilayer sheet formed of the resin composition (II) in an amount of up to 500 parts by weight. 2. A fire-resistant multi-layer sheet comprising a layer A having a thickness of 0.5 to 10 mm and a layer C having a thickness of 0.01 to 2 mm laminated on at least one surface of the layer A, wherein the layer A is formed of a thermoplastic resin. 100 to 100 parts by weight of resin and / or rubber substance, 20 to 500 in total amount of phosphorus compound and neutralized heat-expandable graphite
Parts by weight, 10 to 500 parts by weight of a hydrated inorganic substance, and 10 to 500 parts by weight of a metal carbonate, and the weight ratio of the neutralized thermally expandable graphite to the phosphorus compound is 0.01 to 500 parts by weight.
9, wherein the C layer is composed of 100 parts by weight of a thermoplastic resin and / or a rubber substance, 20 to 300 parts by weight of a phosphorus compound, and 10 to 480 of a metal carbonate.
A fire-resistant multilayer sheet comprising a resin composition (III) containing at least 30 parts by weight and having a total amount of a phosphorus compound and a metal carbonate of 30 to 500 parts by weight.