JP2000159903A - Fireproof resin sheet and laminate thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a fireproof resin sheet excellent in fire resistance, water resistance and workability, and a laminate thereof. SOLUTION: This resin sheet is made from a fireproof resin composition containing a thermoplastic resin and/or a rubbery resin, a phosphor compound, a thermally expandable graphite treated for neutralization, a hydrated inorganic substance and at least one kind selected from alkali metal salts, alkaline earth metal salts, metal salts of the metals belonging to the group IIa of the Periodic Table and metal salts of the metals belonging to the group III of the Periodic Table. When the resin sheet is subjected to perfect combustion under heating conditions of 50 kW/m2, the ratio (D1/D0) between the thickness (D0) before heating and the thickness (D1) after heating is 1.1-20; and when a circular pressure probe of 0.25 cm2 in diameter is allowed to touch the combustion residue after the perfect combustion and a load is applied at a speed of 0.1 cm/sec, the difference of the maximum load and the minimum load in a continued displacement-load curve is 0.01 kg/cm2 or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fire-resistant resin sheet and a laminate thereof.

[0002]

2. Description of the Related Art In order to impart fire resistance to a building, a material coated or applied to the building is called a refractory material. In order for such a refractory material to retain fire resistance during combustion, it not only incinerates during combustion but also forms carbide (combustion residue), and furthermore, the combustion residue is retained without collapse during combustion. Therefore, the shape retention of the combustion residue becomes important.

A composition used for the refractory material is disclosed in, for example, Japanese Patent Publication No. 63-7238. However, when this composition is used for a vertical portion, the shape of the combustion residue remaining after combustion becomes brittle,
In some cases, sufficient fire resistance was not exhibited.

On the other hand, when the composition of the composition is determined with emphasis on the shape retention of the combustion residue, there is a problem that the water resistance is poor and the long-term performance is poor.

[0005] Examples of such compounds include, for example, polyhydric alcohols widely used as a carbonization accelerator in fire-resistant paints. Since this polyhydric alcohol generally has a very high solubility in water, the water resistance of the refractory paint may be reduced, and it has been difficult to use the polyhydric alcohol for applications exposed on the surface.

In the case of fire-resistant paints used for buildings,
Generally, a fire-resistant paint is coated with a surface coat to impart water resistance.However, the work is a double-coating operation on site, and it is necessary to air-dry and cure each time it is applied. There was a problem that workability was poor.

[0007]

SUMMARY OF THE INVENTION In view of the foregoing, it is an object of the present invention to provide a fire-resistant resin sheet excellent in fire resistance (particularly shape retention of combustion residue), water resistance and workability, and a laminate thereof. Is to do.

[0008]

The fire-resistant resin sheet according to the first aspect of the present invention (hereinafter referred to as the first invention) comprises a thermoplastic resin and / or a rubber-based resin, a phosphorus compound,
Neutralized heat-expandable graphite, hydrous inorganics, and
A resin sheet comprising a refractory resin composition containing at least one selected from an alkali metal salt, an alkaline earth metal salt, a metal salt of a metal belonging to Group IIa of the periodic table and a metal salt of a metal belonging to Group III of the periodic table. Then, the resin sheet
When completely burned under the heating condition of 0 kW / m ₂ , the ratio (D ₁ ) of the thickness before heating (D ₀ ) to the thickness after heating (D ₁ )
/ D ₀ ) is 1.1 to 20, and a displacement load when a load is applied at a speed of 0.1 cm / sec by bringing a circular indenter having a diameter of 0.25 cm ₂ into contact with the combustion residue after complete combustion. In the curve, the difference between the continuous maximum load and the minimum load is 0.0
It is at least 1 kg / cm ₂ .

The fire-resistant resin sheet laminate according to the invention of claim 2 of the present application (hereinafter referred to as the second invention) has a layer of the fire-resistant resin sheet (A) of the first invention and a thickness of 40 mm in accordance with JIS Z0208. Water vapor permeability measured at 90 ° C and 90% RH is 10
A fire-resistant resin sheet laminate comprising a resin sheet (B) layer having a thickness of less than g / m ₂ · 24 h, wherein the resin sheet (A) layer has a thickness of 0.5 to 10 mm, (B) The thickness of the layer is 0.01 to 2 mm, and the ratio of the thickness of the resin sheet (A) layer to the thickness of the resin sheet (B) layer [resin sheet (A) layer / resin sheet ( B) Layer]
Is 1 to 1,000.

The refractory resin sheet (A) used in the present invention comprises a thermoplastic resin and / or a rubber-based resin, a phosphorus compound, a neutralized heat-expandable graphite, a hydrated inorganic substance, an alkali metal salt, and an alkali metal salt. Earth metal salts, periodic table II
It is formed from a refractory resin composition containing at least one selected from a metal salt belonging to Group a and a metal salt belonging to Group III in the periodic table.

The thermoplastic resin and / or rubber resin 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, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR) ), 1,2-polybutadiene rubber (1,2-BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), nitrile rubber (NBR), butyl rubber (IIR), ethylene-propylene rubber (EPM, EPDM) , Chlorosulfonated polyethylene (C M), acrylic rubber (ACM, AN
M), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluoro rubber (F
KM, FZ), urethane rubber (U) and the like, and these may be used alone or in combination of two or more. Further, a blend of two or more resins may be used as a base resin in order to adjust the melt viscosity, flexibility, adhesiveness, and the like of the resin.

Halogenated resins such as the above-mentioned chloroprene-based resins and chlorinated butyl-based resins have high flame retardancy by themselves, crosslink occurs by a dehalogenation reaction by heat, and the strength of the residue after heating is improved. It is preferred in that respect. The thermoplastic resin and / or rubber component exemplified above is very flexible and has rubber-like properties, and thus can be highly filled with a metal salt or the like described below. ) Is flexible and flexible.
In order to obtain a more flexible and flexible resin sheet (A), a non-vulcanized rubber or a polyethylene resin is preferably used.

As the polyethylene resin, for example,
Ethylene homopolymer, copolymer containing ethylene as a main component, a mixture thereof, ethylene-vinyl acetate copolymer,
Examples include an ethylene-ethyl acrylate copolymer and an ethylene-methacrylate copolymer. Examples of the copolymer containing ethylene as a main component include, for example, copolymers of ethylene containing ethylene portion as a main component and another α-olefin.
Hexene, 4-methyl-1-pentene, 1-octene,
Examples thereof include 1-butene and 1-pentene.

The thermoplastic resin and / or the rubber-based resin may be cross-linked or modified as long as the fire resistance is not impaired. The timing at which the thermoplastic resin and / or the rubber-based resin is crosslinked or modified is not particularly limited, and a thermoplastic resin and / or a rubber-based resin which has been previously crosslinked and modified may be used. Crosslinking or modification may be performed at the same time when the components are blended, or crosslinking or modification may be performed after blending a phosphorus compound or other components with a thermoplastic resin and / or a rubber-based resin. May go.

The method for crosslinking the thermoplastic resin and / or the rubber-based resin is not particularly limited, and a crosslinking method usually performed for a thermoplastic resin or a rubber-based resin, for example,
Cross-linking using various cross-linking agents, peroxides, and the like; a cross-linking method by electron beam irradiation, and the like. As for the non-vulcanized rubber, vulcanization may be performed after blending a phosphorus compound, neutralized heat-expandable graphite, and other components.

[0016] A tackifier may be added to the thermoplastic resin and the rubber-based resin. Examples of the tackifier include a tackifier resin, a plasticizer, oils and fats, and a low-polymer polymer. As the tackifying resin, for example,
Rosin, rosin derivative, dammar, copal, cumarone / indene resin, polyterpene, non-reactive phenol resin, alkyd resin, petroleum hydrocarbon resin, xylene resin, epoxy resin and the like.

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. Further, from the viewpoints of performance, safety, cost, and the like, ammonium polyphosphate is preferred. Are more preferred.

[0018]

Embedded image

In the formula, R ₁ and R ₃ are hydrogen, C ₁ -C 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.

[0020] 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 those obtained by coating the surfaces of red phosphorus particles with a resin are preferably used from the viewpoint of moisture resistance and safety such as not spontaneously igniting during kneading.

The above ammonium polyphosphates include:
Not particularly limited, for example, ammonium polyphosphate, melamine-modified ammonium polyphosphate and the like,
Particularly, ammonium polyphosphate is preferably used from the viewpoints of flame retardancy, safety, cost and the like. Commercially available products include, for example, “AP422” and “AP462” manufactured by Hoechst; “Sumisafe P” manufactured by Sumitomo Chemical; “Terage C60”, “Terage C70”, and “Terage C8” manufactured by Chisso.
0 "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-butylphosphonic 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 above-mentioned heat-expandable graphite is a natural scale-like graphite, pyrolytic graphite, powder such as Kish 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, hydrogen peroxide, etc. Is a crystalline intercalation compound that maintains the 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 is obtained.

The aliphatic lower amine is not particularly restricted but includes, for example, monomethylamine, dimethylamine, trimethylamine, ethylamine, propylamine, butylamine and the like.

The above-mentioned alkali metal compound and alkaline earth metal compound are not particularly restricted but include, for example, hydroxides, oxides, carbonates, sulfates and organic acid salts of potassium, sodium, calcium, barium, magnesium and the like. And the like.

The particle size of the neutralized heat-expandable graphite is preferably 20 to 200 mesh. Particle size is 200
When the mesh size is smaller than the mesh, the expansion degree of the heat-expandable graphite is small and a predetermined refractory heat insulating layer cannot be obtained. When the mesh size is larger than 20 mesh, there is an advantage that the expansion degree of the heat-expandable graphite is large. When kneading, the dispersibility deteriorates, and a decrease in physical properties is inevitable.

Commercial products of the neutralized heat-expandable graphite include, for example, "CA-60S" manufactured by Nippon Kasei Co., Ltd. and "GREP-EG" manufactured by Tosoh Corporation.

Examples of the above-mentioned hydrated inorganic substances include aluminum hydroxide, calcium hydroxide, magnesium hydroxide and the like. Magnesium hydroxide and aluminum hydroxide are different in the temperature range in which the dehydration effect is exhibited.
It is preferable to use them together because a more effective temperature rise suppressing effect can be obtained.

The metal salt is, for example, at least one selected from alkali metal salts, alkaline earth metal salts, metal salts belonging to Group IIa of the periodic table and metal salts belonging to Group III of the periodic table. Examples of the metal salt include, but are not particularly limited to, metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, and strontium carbonate; talc,
Mica, calcium diphosphate, gypsum and the like are preferably used.

The metal salt itself is decarbonated at a low temperature and foams and expands due to the presence of the phosphorus compound. Therefore, the metal salt is preferable from the viewpoint of improving expandability. Further, calcium diphosphate, gypsum and the like are also preferable because they have self-expanding properties.

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

The metal salt has a particle size of 1 to 20 μm.
Is preferred. When the particle size is less than 1 μm, secondary agglomeration occurs and dispersibility deteriorates. When the particle size exceeds 20 μm, the fire-resistant resin composition does not effectively act as an aggregate at the time of burning. descend.

The above-mentioned hydrated inorganic substance tends to inhibit the expansion of the refractory resin composition during combustion. When added in a large amount, the shape retention is improved, but the expansion ratio is undesirably reduced. In addition, the metal salt effectively acts as an aggregate at the time of burning the refractory resin composition, improves shape retention of combustion residue, and does not hinder expansion.

Examples of commercially available aluminum hydroxide include "H-42M" having a particle size of 1 μm (manufactured by Showa Denko KK) and "H-31" having a particle size of 18 μm (manufactured by Showa Denko KK). In addition, as commercial products of calcium carbonate,
For example, "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.) are exemplified. Further, it is more preferable to use a combination of a large particle size and a small particle size, and the combination can further increase the packing.

In the refractory resin composition, the compounding amount of the phosphorus compound and the neutralized heat-expandable graphite is 100 parts by weight of a thermoplastic resin and / or a rubber-based resin (hereinafter referred to as a resin component). And the total amount of the two components is 20
~ 300 parts by weight are preferred. If the amount is less than 20 parts by weight, sufficient fire resistance cannot be obtained because the amount of the residue after heating is insufficient. If the amount exceeds 300 parts by weight, the mechanical properties are greatly reduced, and the material cannot be used.

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 in the above range, it is possible to obtain shape retention of combustion residues and high fire resistance. When the compounding ratio of the heat-expandable graphite subjected to the neutralization treatment increases, the graphite expanded at the time of combustion scatters,
A sufficient expanded heat insulating layer cannot be obtained. In addition, when the compounding ratio of the phosphorus compound increases, formation of the heat insulating layer becomes insufficient, so that a sufficient heat insulating effect cannot be obtained.

In the refractory resin composition, the amount of the water-containing inorganic substance and the metal salt is preferably 50 to 500 parts by weight as a total amount of the two components with respect to 100 parts by weight of the resin component. If the compounding amount is less than 50 parts by weight, sufficient fire resistance cannot be obtained, and if it exceeds 800 parts by weight, the mechanical properties are greatly reduced and it cannot be used.

Further, the weight ratio of the hydrated inorganic substance to the metal salt (hydrated inorganic substance / metal salt) is preferably from 0.33 to 3.
When the weight ratio is less than 0.33, the endothermic effect due to dehydration is not sufficiently exhibited, and when it exceeds 3, the shape retention of combustion residues, which is exhibited due to the presence of the metal salt, is insufficient, and the fire resistance is reduced.

The resin sheet (A) obtained from the refractory resin composition, when completely burned under a heating condition of 50 kW / m ₂ , has a thickness before heating (D ₀ ) and a thickness after heating (D ₀ ).
₁ ) and the ratio (D ₁ / D ₀ ) is 1.1 to 20.

When D ₁ / D ₀ is less than 1.1, the thermal conductivity after combustion hardly decreases as compared with that before combustion, and therefore, in order to obtain sufficient heat insulating performance, the thickness (D ₀ ) before heating is obtained. When the thickness exceeds 20, the shape of the combustion residue is not maintained at all. Therefore, when used in a vertical application, the combustion residue after the combustion collapses and a sufficient heat insulating effect cannot be exhibited.

Further, the resin sheet has a displacement load curve when a load is applied at a speed of 0.1 cm / sec by bringing a circular indenter having a diameter of 0.25 cm ₂ into contact with the combustion residue after complete combustion. The difference between the continuous maximum load and the minimum load is limited to 0.01 kg / cm ₂ or more.

The difference between the maximum load and the minimum load is 0.01
If it is less than kg / cm ₂ , the shape of the combustion residue is not maintained, so that when used in a vertical application, sufficient fire resistance is not exhibited, and the application is limited.

The above displacement load curve was measured by using a finger feeling tester (manufactured by Kato Tech Co., Ltd.) to bring a circular indenter having a diameter of 0.25 cm ₂ into contact with the combustion residue.
It is measured with a load applied at a speed of cm / sec. A material that foams and expands during combustion has large and small bubbles in the combustion residue after combustion and has bubble cells. It is considered that the breaking strength of the bubble cell itself is reflected in the difference between the continuous maximum load and the minimum load in the displacement load curve.

As the resin sheet (B), JIS
There is no particular limitation as long as the moisture permeability measured at 40 ° C. and 90% RH according to Z0208 is less than 10 g / m ₂ · 24 h. If the moisture permeability is 10 g / m ₂ · 24 h or more, sufficient water resistance cannot be obtained, and the long-term performance of the resin sheet (B) may be deteriorated.

As the resin sheet (B), for example,
Paper, woven fabric, nonwoven fabric, film, metal foil, metal thin plate, vapor-deposited film, composite sheet of metal foil and resin film, resin sheet composed of the above resin, resin sheet containing an inorganic filler added to the above resin; inorganic fiber A sheet or the like is used.

Examples of the paper include kraft paper, Japanese paper, K-liner paper, and the like. It may be used as a non-combustible paper highly filled with aluminum hydroxide or calcium carbonate, or a flame-retardant paper containing or coated with a flame retardant. In addition, fire resistance can be further improved by using rock wool, ceramic wool, inorganic fibers such as glass fibers, and carbon fibers.

As the non-woven fabric, a wet non-woven fabric made of polypropylene, polyester, nylon, cellulose fiber and the like, a long-term non-woven fabric and the like can be used. Weighing of nonwoven fabric is preferably from 8~500g / m _2, more preferably from 10 to 400 g / m _2. Although it depends on the thickness of the molded body, if the weight is less than 8 g / m ₂ , the molded body is easily broken.

As the above-mentioned film, polyethylene, polypropylene, polyester, polyamide, nylon,
A plastic film such as acrylic is used.

Examples of the metal foil include an aluminum foil, a copper foil and a brass foil. Examples of the metal sheet include aluminum, iron, and stainless steel.

Examples of the above-mentioned vapor-deposited film include an aluminum-deposited film, a silica-deposited film, and a silver-deposited film.

Examples of the composite sheet of the metal foil and the resin film include those obtained by laminating a resin film on one or both sides of an aluminum foil.

In order to impart watertightness to the resin sheet (B), a sheet made of butyl rubber may be used. The butyl rubber sheet is suitable without impairing the external appearance, since the butyl rubber sheet follows the pushing direction of the screw or the screw even when the screw or the screw is used when the fire resistant resin multilayer sheet described later is applied.

The amount of the inorganic filler added to the resin sheet (B) is from 20 to 800 based on 100 parts by weight of the resin.
Parts by weight are preferred. When the resin sheet (A) and the resin sheet (B) are laminated by hot pressing, it is preferable to use the same filler for both resin sheets from the viewpoint of adhesiveness.

As the above-mentioned inorganic fiber sheet, for example, a sheet made of glass fiber, cellulose fiber, ceramic wool fiber, rock wool fiber, woven fabric, non-woven fabric and the like are used. These inorganic fiber sheets may be laminated with thin aluminum layers.

The inorganic filler is not particularly restricted but includes, for example, talc, calcium carbonate, aluminum hydroxide, magnesium hydroxide and the like. Aluminum hydroxide, hydrated inorganic substances such as magnesium hydroxide, endothermic occurs due to water generated by the dehydration reaction at the time of heating, the point that the temperature rise is reduced and high heat resistance is obtained,
Oxide remains as a heating residue, which is particularly preferable in that it functions as an aggregate to improve the strength of the residue.

The fire-resistant resin sheet laminate of the present invention is obtained by laminating a resin sheet (A) layer and a resin sheet (B) layer. The configuration of the fire-resistant resin sheet laminate may be any of a two-layer laminate of A / B, a three-layer laminate of B / A / B, and A / B / A. / A /
B, at the interface and outside of the A / B / A laminate, as a holding material,
The above-mentioned inorganic fiber sheet, metal plate, wire mesh, etc. may be laminated. Further, on the resin sheet (A) layer side, a resin foam or the like that shrinks at the time of combustion may be laminated in order to secure an allowance for expansion.

The thickness of the resin sheet (A) layer is 0.5
10 to 10 mm is preferred. If the thickness is less than 0.5 mm, the initial thickness is small and the heat transfer rate is high, so that a rapid temperature rise occurs before expansion during combustion, and sufficient fire resistance cannot be exhibited. On the other hand, if the thickness exceeds 10 mm, the workability is poor, and it is difficult to secure a space from the viewpoint of building design.

The metal plate and wire mesh are not particularly limited, but include lath wire mesh, stainless steel plate, zinc alloy plated steel plate, aluminum plate, titanium plate, enameled steel plate, fluororesin coated steel plate, clad steel plate, copper plate, surface treated steel plate and the like. Is mentioned.

The resin foam used to secure the expansion margin is not particularly limited, but examples include phenol foam, isocyanurate foam, polyethylene foam and the like. Further, a honeycomb sheet may be used instead of the resin foam.

The thickness of the resin sheet (B) layer is 0.0
1-2 mm is preferred. When the thickness is less than 0.01 mm, a sufficient heat absorbing effect is not exhibited. When the thickness is more than 2 mm, heat is generated because the resin sheet (B) layer burns, and the fire resistance performance of the resin sheet (A) layer is reduced.

The thickness ratio of the resin sheet (A) layer to the resin sheet (B) layer (the resin sheet (A) layer / the resin sheet (B) layer) may be 1 to 1,000. preferable. If the thickness ratio is less than 1, the resin sheet (B) layer will burn and generate heat to reduce the fire resistance of the resin sheet (A) layer, and if it exceeds 1,000, work with nails, screws, etc. In this case, since the thickness of the resin sheet (B) layer following the nails and screws is insufficient, sufficient water resistance cannot be provided.

The method for forming the resin sheet (A) layer and the layer (B) is not particularly limited, and any method can be adopted as long as it is a method for forming a normal resin sheet. For example, extrusion molding, calender molding And hot press molding. In order to obtain a fire-resistant resin sheet laminate in which the resin sheet (A) layer and the layer (B) are laminated, the resin sheet (A) layer and the resin sheet (A) layer may be extruded in one step. The (B) layer may be separately formed and then compression-bonded by a hot press, or may be laminated by lamination at the time of construction. An acrylic adhesive, an epoxy adhesive, or the like is used for bonding at the time of construction.

[0065]

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.

(Examples 1 to 4)
Resin content, hydrogenated petroleum resin, phosphorus compound (ammonium polyphosphate), neutralized heat-expandable graphite, hydrous inorganic substances (aluminum hydroxide, magnesium hydroxide) and inorganic carbonates (calcium carbonate, strontium carbonate) The mixture was supplied to a twin-screw extruder, kneaded and extruded to obtain a fire-resistant resin sheet (A).

(Examples 5 to 8)
Resin content, hydrogenated petroleum resin, phosphorus compound (ammonium polyphosphate), neutralized heat-expandable graphite, hydrous inorganic substances (aluminum hydroxide, magnesium hydroxide) and inorganic carbonates (calcium carbonate, strontium carbonate) The mixture was supplied to a twin-screw extruder, kneaded and extruded to obtain resin sheets (A) and (B). The obtained resin sheets (A) and (B) are pressed and laminated by a hot press,
A fire-resistant resin sheet laminate was obtained.

(Comparative Examples 1 to 3)
The resin component, hydrogenated petroleum resin, phosphorus compound (ammonium polyphosphate), neutralized heat-expandable graphite, and hydrated inorganic material (aluminum hydroxide) are supplied to a twin-screw extruder to be kneaded and extruded. Then, a resin sheet was obtained.

The (fire-resistant) resin sheet and the
And fire-resistant resin sheet laminate as samples,
The results are shown in Tables 1 to 3. (1) Expansion magnification A test piece obtained by cutting a sample to 10 cm x 10 cm is set horizontally.
With the corn calorimeter (ATLAS)
50 kW / m using "CONE2A" _TwoIrradiation
While heating with heat, ignite by spark and complete combustion
After heating, the thickness of the combustion residue was measured, and the thickness before heating (D
₀ ) And thickness after heating (D₁) And expansion ratio
(D₁/ D₀) Was calculated.

(2) Fire resistance A test piece obtained by cutting a sample into the same size was placed on the back surface of a SUS plate having a thickness of 10 cm × 10 cm × 0.5 mm and placed vertically with a cone calorimeter (ATLAS).
Using “CONE2A” manufactured by the company, the SUS plate side was left facing the heating source for 1 hour while being heated with the irradiation heat of 80 kW / m ₂ , and the back surface temperature after 1 hour was measured.

(3) Moisture Permeability Measured at 40 ° C. and 90% RH in accordance with JIS Z0208.

(4) Breaking strength of combustion residue A cone calorimeter (A) was placed in a state where a test piece obtained by cutting a sample to a thickness of 10 cm × 10 cm × 3 mm was horizontally set.
TLAS “CONE2A”), 50 kW /
The mixture was heated with an irradiation heat of m ₂ and completely burned to obtain a combustion residue. Using a finger feeling tester (manufactured by Kato Tech Co.), this combustion residue was brought into contact with a circular indenter having a diameter of 0.25 cm ₂ to apply a load at a speed of 0.1 cm / sec. The difference between the continuous maximum load and minimum load was taken as the breaking strength of the combustion residue (bubble cell).

(5) Breaking strength of combustion residue after immersion in water The burning residue obtained in the same manner as in (4) above was immersed in ion-exchanged water at normal temperature for 3 weeks, and then the breaking strength in the same manner as in (4) above Was measured.

(6) Change rate of expansion ratio after immersion in water The same test piece as in the above (1) was placed in ion-exchanged water at room temperature for 3 hours.
After immersion for a week, complete combustion was performed in the same manner as in (1) above, the expansion ratio was calculated, and the rate of change with respect to the expansion ratio before immersion in water was determined. Rate of change (%) = (expansion magnification after immersion in water / expansion magnification before water immersion) × 100 When the rate of change was 3% or less, it was evaluated as ○.

(7) Fire resistance after immersion in water A test piece similar to the above (1) was placed in ion-exchanged water at room temperature for 3 hours.
After immersion for a week, the back surface temperature after heating for 1 hour in the same manner as in (2) above was measured.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

The components used in the table are as follows. [Resin content]-Metallocene PE (polyethylene): "EG8200" manufactured by Dow Chemical Company-Butyl rubber: "Butyl 065" manufactured by Exxon Corporation-Polybutene: "Polybutene 300 manufactured by Idemitsu Petrochemical Co., Ltd."
R "[hydrogenated petroleum resin]-" Escolez 5320 "manufactured by Exxon [phosphorus compound]-Ammonium polyphosphate:" AP4 "manufactured by Clariant
22 "[Thermal expandable graphite]-" GREP-EG "manufactured by Tosoh Corporation [Hydrophilic inorganic substance]-Aluminum hydroxide:" H-42M "manufactured by Showa Denko KK-Magnesium hydroxide:" Kisma 5B "manufactured by Kyowa Chemical Co., Ltd. [Inorganic Carbonate]-Calcium carbonate: "Whiteton B" manufactured by Shiraishi Calcium Co., Ltd.
F300 ”・ Strontium carbonate: Sakai Chemical

[0080]

The fire-resistant resin sheet of the present invention has the above-described structure, and the combustion residue foamed and expanded at the time of combustion retains its shape, lowers the thermal conductivity, and exhibits excellent fire resistance. Further, the fire-resistant resin sheet laminate in which the fire-resistant resin sheet (A) and the resin sheet (B) having a specific moisture permeability are combined is easy to construct and excellent in water resistance, so that it can be used in various applications. In the above, the initial fire resistance can be maintained for a long period of time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 21/00 C08L 21/00 101/00 101/00 (72) Inventor Kazuhiro Okada Mishimakorishima, Osaka 2-1 Momoyama Honmachi Sekisui Chemical Co., Ltd.F-term (reference) 4F100 AA01A AA04 AA08 AA18 AA19 AD11A AK01A AK01B AK02 AK04 AK09B AK09J AK28B AK28J AL01B AN02B BA02 DJ04A GB07 JA20A JA20B JB06 JB16A JD04B JJ01 JJ07A JL05 YY00A YY00B 4J002 AC011 AC031 AC041 AC061 AC071 AC081 AC091 AC111 AE005 BB031 BB051 BB061 BB071 BB111 BB151 BB171 BB181 BB241 BB271 BC021 BD031 BD121 BG001 BG041 BN151 CG001 CH041 CH071 CK021 CL001 CP031 DA027 DA056 DE078 DE088 DE148 D E239 DE249 DG059 DH046 DH049 DH056 DJ049 DJ059 EK000 EW046 EW126 FB077 FD020 FD138 FD140 FD340 GF00 GL00

Claims (3)

[Claims] 1. A thermoplastic resin and / or a rubber-based resin, a phosphorus compound, a neutralized heat-expandable graphite, a hydrated inorganic substance,
A resin comprising a refractory resin composition containing at least one selected from an alkali metal salt, an alkaline earth metal salt, a metal salt of a metal belonging to Group IIa of the periodic table, and a metal salt of a metal belonging to Group III of the periodic table. When the resin sheet is completely burned under a heating condition of 50 kW / m ₂ , the ratio (D ₁ / D) of the thickness (D ₀ ) before heating and the thickness (D ₁ ) after heating is obtained. ₀ ) is 1.1 to 20 and a displacement load curve when a circular indenter having a diameter of 0.25 cm ₂ is brought into contact with the combustion residue after complete combustion and a load is applied at a speed of 0.1 cm / sec. And a difference between a continuous maximum load and a minimum load is 0.01 kg / cm ₂ or more. 2. The fire-resistant resin sheet (A) according to claim 1.
Layer, 40 ° C., 90% R according to JIS Z0208
A fire-resistant resin sheet laminate obtained by laminating a resin sheet (B) layer having a moisture permeability measured in H of less than 10 g / m ₂ · 24 h, wherein the resin sheet (A) layer has a thickness of 0 0.5 to 10 mm, and the thickness of the resin sheet (B) layer is 0.5 to 10 mm.
And the ratio of the thickness of the resin sheet (A) layer to the thickness of the resin sheet (B) layer [resin sheet (A) layer / resin sheet (B) layer] is 1 to 1, 000. 3. The fire-resistant resin sheet laminate according to claim 2, wherein the resin sheet (B) layer is made of butyl rubber.