JP2022171059A - Laminate for extinguishing fire and method for producing laminate for extinguishing fire - Google Patents

Abstract

To provide a laminate for extinguishing fire having resistance to e.g. the impact of an explosion in the event of a fire.SOLUTION: A laminate for extinguishing fire has: a fiber layer containing organic fiber or inorganic fiber having high-intensity heat resistance, and a resin layer. At least one of the fiber layer and the resin layer contains a fire extinguisher component that generates aerosol by combustion.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a fire-extinguishing laminate and a method for manufacturing a fire-extinguishing laminate.

BACKGROUND ART An automatic fire extinguishing device having a bag formed of a synthetic resin film and a fire extinguishing agent enclosed in the bag is known (for example, Patent Document 1).

WO2018/012503

However, the device described in Cited Document 1 does not have sufficient resistance to the impact caused by an explosion or the like during a fire.

The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a fire-extinguishing laminate having resistance to impact due to an explosion or the like during a fire. Moreover, this indication aims at providing the manufacturing method of the said fire-fighting laminated body.

A fire-extinguishing laminate according to one aspect of the present disclosure includes a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance, and a resin layer, and at least one of the fiber layer and the resin layer is Contains aerosol-generating extinguishing agent components.

By installing the fire-extinguishing laminate in a portion where there is a risk of ignition, the aerosol fire-extinguishing agent can be immediately filled in the surroundings by the heat generated by ignition or until ignition. In addition, even if an impact such as an explosion occurs due to ignition, the fire-extinguishing function of the fire-extinguishing laminate is unlikely to be impaired. This allows the fire to be extinguished in a short period of time and prevent the fire from spreading to the surrounding area. In addition, the above-described fire-extinguishing laminate is excellent in terms of safety, since initial fire-extinguishing can be performed without direct intervention of human hands when a fire occurs.

In one aspect, the fiber layer may contain at least one selected from the group consisting of carbon fiber, glass fiber, metal fiber and ceramic fiber.

In one aspect, the thickness of the fibrous layer may be from 0.02 to 2.0 mm.

In one aspect, the resin layer may contain at least one selected from the group consisting of urethane resins, epoxy resins, silicone resins, vinyl chloride resins, polyolefin resins, and polyester resins.

A method for manufacturing a fire-extinguishing laminate according to one aspect of the present disclosure is any of the following.
A step of impregnating a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol by combustion; and impregnating the first liquid composition. A manufacturing method comprising a step of drying an object, a step of applying a second liquid composition containing a liquid component and a resin onto a fiber layer, and a step of drying the applied second liquid composition.
a step of applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin onto a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance; and drying the liquid composition.
A step of impregnating a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol by combustion; and impregnating the first liquid composition. a step of drying an object; a step of applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin onto the fiber layer; and drying the applied third liquid composition. A manufacturing method comprising:

According to the present disclosure, it is possible to provide a fire-extinguishing laminate having resistance to impact such as an explosion during a fire. Further, according to the present disclosure, it is possible to provide a method for manufacturing the fire-extinguishing laminate.

According to the present disclosure, it is possible to maintain its shape even against the impact of an explosion in the event of a fire, etc., it can be easily installed in a part where there is a risk of ignition, and it has an excellent effect in initial fire extinguishing at the time of ignition. There is provided a fire-fighting laminate that exhibits Such fire-extinguishing laminates can be suitably used as industrial materials such as building materials, automobile members, aircraft members, and electronic members.

FIG. 1 is a schematic cross-sectional view of a fire-extinguishing laminate according to one embodiment.

Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments.

<Laminate for fire extinguishing>
The fire-extinguishing laminate includes a fiber layer and a resin layer. At least one of the fiber layer and the resin layer contains a fire extinguishing agent component that generates an aerosol by combustion. FIG. 1 is a schematic cross-sectional view of a fire-extinguishing laminate according to one embodiment. The fire extinguishing laminate 10 includes a fiber layer 1 and a resin layer 2 in this order.

The thickness of the fire-extinguishing laminate is not necessarily limited because it varies depending on the layer structure. It can be 20 mm.

The area of the main surface of the fire-extinguishing laminate (the surface when the fire-extinguishing laminate is viewed from above in the vertical direction) can be, for example, 1 to 1,500 cm ² from the viewpoint of fire-extinguishing performance, impact resistance, and handleability. .

(fiber layer)
The fiber layer contains organic fibers or inorganic fibers having high strength and heat resistance, and specifically contains at least one of organic fibers and inorganic fibers. Examples of organic fibers include carbon fibers. Examples of inorganic fibers include glass fibers, metal fibers (eg, stainless steel fibers and aluminum fibers), ceramic fibers, and the like. These fibers have high strength and heat resistance. The fiber layer may be a fiber sheet in which fibers arranged in one direction are fixed with a resin, or may be a woven fiber fabric, a knitted fiber fabric, or the like. A layer made of fibers (especially woven fabric or knitted fabric) can easily carry a sufficient amount of fire extinguishing agent components, is lightweight, and is resistant to deterioration due to heat and impact during ignition and can easily maintain strength. This makes it possible to further ensure safety. The fibrous layer may include multiple layers containing different fibers.

The fiber layer is a substrate having high strength and heat resistance that can withstand the heat and impact of fire. Therefore, the fiber layer can be said to be a high-strength heat-resistant substrate. The high-strength heat-resistant substrate has at least the following tensile strength and heat resistance temperature.

The tensile strength of the fiber layer measured according to JIS-R-3420 may be 5×10 ³ N/25 mm or more, and may be 50×10 ³ N/25 mm or more. Although the upper limit of the tensile strength is not particularly limited, it can be 1×10 ⁶ N/25 mm or less. Tensile strength can be the average of both the machine direction MD and the normal direction TD if the fiber layer has both.

The elastic modulus of the fiber layer measured according to JIS-R-3414 may be 3 GPa or more, may be 10 GPa or more, or may be 50 GPa or more. Although the upper limit of the elastic modulus is not particularly limited, it can be 300 GPa or less. The modulus can be the average of the machine direction MD and the normal direction TD if the fiber layer has both.

The heat resistance temperature of the fiber layer measured according to ISO15025 may be 300° C. or higher, may be 700° C. or higher, or may be 1300° C. or higher. Although the upper limit of the heat resistance temperature is not particularly limited, it can be 1400° C. or less.

The thickness of the fiber layer can be 0.02 to 2.0 mm, and may be 0.4 to 1.0 mm, from the viewpoint of tensile strength, flexibility, installation space, cost, and the like.

When the fiber layer contains a fire extinguishing agent component that generates an aerosol by combustion, the amount of the fire extinguishing agent component can be 10 to 80% by mass with respect to the total amount of the fiber layer from the viewpoint of fire extinguishing ability and fire extinguishing agent retention. , 20 to 70% by weight.

(resin layer)
The resin layer is a layer that imparts various functions to the fire-extinguishing laminate, and can be called a functional layer. The functional layer includes an abrasion resistant layer (hard coat layer), an antifouling layer, a water-repellent layer, a decorative layer, an ultraviolet absorbing layer, a heat transferable layer, and the like. What kind of function is imparted to the fire-extinguishing laminate can be adjusted depending on the resin to be used. The resin layer may contain a plurality of these configurations.

Examples of resins constituting the resin layer include urethane resins, epoxy resins, silicone resins, vinyl chloride resins, polyolefin resins (polyethylene and polypropylene), polyester resins, and the like. These resins exhibit a predetermined function while being stably fixed in the functional layer under normal conditions, and readily readily supply thermal energy to the extinguishing agent component in the event of an abnormal fire outbreak. When the resin layer contains a fire extinguishing agent component that generates an aerosol by combustion, these resins (especially epoxy resins) have good compatibility with the extinguishing agent component and can also function as a binder for the extinguishing agent component.

The thickness of the resin layer can be 0.050 to 1 mm, and may be 0.1 to 0.3 mm, from the viewpoints of fire extinguishing function, flexibility, installation space, cost, and the like.

When the resin layer contains a fire extinguishing agent component that generates an aerosol by combustion, the amount of the fire extinguishing agent component can be 60 to 97% by mass with respect to the total amount of the resin layer from the viewpoint of fire extinguishing ability and coatability. , 70 to 93% by weight.

The resin layer may contain other components such as a dispersant, a coloring agent, an antioxidant, a flame retardant, an inorganic filler, and an adhesive. The content of other components in the resin layer can be 20 parts by mass or less with respect to 100 parts by mass of the total amount of the resin layer.

(Fire extinguishing agent component)
The extinguishing agent component generates an aerosol upon combustion. The fire extinguishing agent component includes, for example, at least an inorganic oxidant and a radical generator. The radical generator has an action (negative catalytic action) of stabilizing combustion radicals and suppressing a chain reaction of combustion.

The inorganic oxidizing agent (hereinafter sometimes referred to as "(A) component") is a component that generates thermal energy by combustion. Inorganic oxidants include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, magnesium chlorate, and potassium perchlorate. Among these, one type may be used alone, or two or more types may be used in combination.

The radical generator (hereinafter sometimes referred to as "(B) component") is a component for generating an aerosol (radical) by thermal energy generated by combustion of the inorganic oxidant. As the radical generator, it is preferable to use one having a decomposition initiation temperature in the range of 90 to 260°C. Radical generators include potassium and sodium salts. As potassium salts, potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, Tetrapotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate and potassium bicarbonate. Sodium salts include sodium acetate, sodium citrate and sodium bicarbonate. Among these, one type may be used alone, or two or more types may be used in combination.

The content of component (A) is, for example, 10 to 60 parts by mass, preferably 20 to 50 parts by mass, more preferably 100 parts by mass of the total amount of components (A) and (B). 35 to 45 parts by mass. The content of component (B) is, for example, 40 to 90 parts by mass, preferably 50 to 80 parts by mass, and more preferably 100 parts by mass as the total amount of components (A) and (B). 55 to 65 parts by mass.

You may use a commercial item as an extinguishing agent component. Commercially available fire extinguishing agent components include K-1 (trade name, manufactured by Yamato Protech Co., Ltd.) and STAT-X (trade name, manufactured by Nippon Koki Co., Ltd.).

A fire extinguishing agent component can be used with a binder resin. Thermoplastic resins and thermosetting resins can be used as binder resins. Polyolefin-based resins such as polypropylene-based resins, polyethylene-based resins, poly(1-)butene-based resins, polypentene-based resins, polystyrene-based resins, acrylonitrile-butadiene-styrene-based resins, methyl methacrylate-butadiene-styrene resins as thermoplastic resins , ethylene-vinyl acetate resin, ethylene-propylene resin, polycarbonate resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin, and the like. Thermosetting resins include 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 (EPR, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM), epichlorohydrin rubber (CO, ECO), polyvulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), urethane rubber (U), polyurethane resin, polyisocyanate resin, polyisocyanurate resin, phenol resin, epoxy resin, and the like. The binder resin may contain a curing agent component.

Epoxy resins are suitable for binder resins because they are highly compatible with fire extinguishing agent components, soluble in alcohol solvents described below, and have high stability. Since epoxy resins are highly compatible with potassium salts and sodium salts (radical generators), it is easy to obtain a fire-extinguishing agent-containing layer having a uniform thickness. In addition, since the epoxy resin does not undergo hydrolysis or embrittlement due to wet heat, the fire-extinguishing agent-containing layer containing the epoxy resin as a binder resin has excellent stability. Further, when the extinguishing agent-containing layer is burned, thermal decomposition begins at about 260 to 350° C., and aerosol can be generated without impairing the extinguishing performance.

The amount of the binder resin can be 5 to 40 parts by mass with respect to 100 parts by mass of the total amount of the extinguishing agent components, from the viewpoint of fixing the extinguishing agent components and exhibiting excellent fire extinguishing performance, and 10 to 30 parts by mass. It can be.

(adhesion layer)
The fire-extinguishing laminate may further comprise an adhesive layer between the fiber layer and the resin layer. The adhesive layer can be formed using, for example, an adhesive such as epoxy resin, acrylic resin, or urethane resin. The thickness of the adhesive layer may be, for example, 1-10 μm, and may be 2-5 μm.

<Method for manufacturing fire-extinguishing laminate>
The fire-extinguishing laminate can be produced, for example, by the following production methods (1) to (3).
(1) A step of impregnating a fiber layer containing organic or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol by combustion; Manufacture comprising a step of drying a liquid composition, a step of applying a second liquid composition containing a liquid component and a resin onto a fiber layer, and a step of drying the applied second liquid composition Method.
(2) a step of applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin onto a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance; and drying the third liquid composition.
(3) a step of impregnating a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol when burned; A step of drying one liquid composition, a step of applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin on the fiber layer, and the applied third liquid composition. and a step of drying the fire-extinguishing laminate.

According to the above (1), a fire-extinguishing laminate including a fiber layer containing a fire-extinguishing agent component and a resin layer can be obtained. (2) makes it possible to obtain a fire-extinguishing laminate comprising a fiber layer and a resin layer containing a fire-extinguishing agent component. According to (3), it is possible to obtain a fire-extinguishing laminate including a fiber layer containing a fire-extinguishing agent component and a resin layer containing a fire-extinguishing agent component. These methods make it possible to manufacture fire-extinguishing laminates in large quantities at low cost.

Liquid components used for preparing each liquid composition include alcohol solvents (eg, ethanol, IPA). An alcohol solvent is suitable as a solvent for preparing a liquid composition because it has excellent dispersibility of fire extinguishing agent components and low volatility. The amount ratio of the liquid component to the amounts of the extinguishing agent component and the resin (binder resin) may be appropriately adjusted so as to obtain the desired viscosity of the liquid composition.

The liquid composition can be used for impregnation or coating as described above. Application can be performed by any suitable method. Application can be performed by a wet film forming method such as gravure coater, dip coater, reverse coater, wire bar coater, and die coater.

Drying of the liquid composition can be carried out by heating the liquid composition at, for example, 50 to 100° C. from the viewpoint of sufficiently removing the liquid component and suppressing the reaction of the extinguishing agent component.

As other manufacturing methods, for example, a fiber layer containing a fire extinguishing agent component and a resin layer containing a fire extinguishing agent component, a fiber layer and a resin layer containing a fire extinguishing agent component, or a fiber layer containing a fire extinguishing agent component and a resin layer containing a fire extinguishing agent component and are respectively prepared and laminated via an adhesive layer.

The present disclosure will be described in more detail by the following examples, but the present disclosure is not limited to these examples.

Materials shown in Table 1 were prepared as the fiber layer.

In Table 1, the tensile strength of each layer was measured according to JIS-R-3420, the elastic modulus was measured according to JIS-R-3414, and the heat resistance temperature was measured according to ISO15025.

<Preparation of fire-extinguishing laminate>
A fire-extinguishing laminate shown in Table 2 was produced. Details for each example are provided below.

(Example 1)
Aerosol fire extinguishing agent K-1 ethanol slurry manufactured by Yamato Protech Co., Ltd. and binder resin (epoxy resin, K468HP92 black manufactured by Toyo Ink Co., Ltd.) are mixed at a solid content mass ratio of binder resin: extinguishing agent = 10:90. A liquid composition was prepared by mixing. This was applied to the fiber layer shown in Table 1 to form a coating film. This was dried at 90° C. for 4 minutes to form a resin layer (decorative layer) having a thickness of 200 μm on the fiber layer. Thus, a fire-extinguishing laminate was obtained.

(Examples 2-4)
A fire-extinguishing laminate was obtained in the same manner as in Example 1, except that the fiber layer was as shown in Table 1.

(Example 5)
Aerosol fire extinguishing agent K-1 ethanol slurry manufactured by Yamato Protech Co., Ltd. and binder resin (epoxy resin, K468HP92 black manufactured by Toyo Ink Co., Ltd.) are mixed at a solid content mass ratio of binder resin: extinguishing agent = 30:70. A liquid composition was prepared by mixing. This was impregnated with the fiber layers shown in Table 1. This was dried at 90° C. for 4 minutes to obtain a fiber layer carrying a fire extinguishing agent component. The amount of the fire extinguishing agent component was 50% by mass with respect to the total amount of the fiber layer.

Next, a binder resin (epoxy resin, K468HP92 black, manufactured by Toyo Ink Co., Ltd.) was added to ethanol to prepare a liquid composition. This was applied to the fiber layer carrying the fire extinguishing agent component to form a coating film. This was dried at 90° C. for 4 minutes to form a functional layer (decorative layer) having a thickness of 200 μm on the fiber layer. Thus, a fire-extinguishing laminate was obtained.

(Examples 6-8)
A fire-extinguishing laminate was obtained in the same manner as in Example 5, except that the amount of the fire-extinguishing agent component relative to the total amount of the fiber layer, the binder resin, and the fiber layer was set as shown in Tables 1 and 2.

(Example 9)
A fiber layer carrying a fire extinguishing agent component was obtained in the same manner as in Example 5. A resin layer (decorative layer) having a thickness of 200 μm was formed on this fiber layer in the same manner as in Example 1. Thus, a fire-extinguishing laminate was obtained.

(Examples 10-12)
A fire-extinguishing laminate was obtained in the same manner as in Example 9, except that the amount of the fire extinguishing agent component relative to the total amount of the fiber layer, the binder resin, and the fiber layer was set as shown in Tables 1 and 2.

(Comparative example 1)
A liquid composition was prepared by adding a binder resin (epoxy resin, K468HP92 black, manufactured by Toyo Ink Co., Ltd.) to ethanol. This was applied to the base material shown in Table 1 to form a coating film. This was dried at 90° C. for 4 minutes to form a functional layer (decorative layer) having a thickness of 200 μm on the substrate. A laminate was thus obtained.

<Combustion falling ball fire extinguishing test>
The fire-extinguishing laminated body obtained in each example was cut into a 70 mm×120 mm square and used as a test sample.
JIS B 2238-1996 Nominal pressure 5K, nominal diameter A32, B11/4, between two SOP type flanges, the above sample is placed on the flange with bolts and nuts so that the center of the sample and the center of the flange match. Fixed.
A stainless steel support tube having an outer diameter of φ32 mm, an inner diameter of φ28, and a length of 1 m was placed so as to be perpendicular to the top of the sample surface.
Ignite 1 g of a candle or solid fuel, and within 3 to 5 seconds after applying the tip of the flame to the lower surface of the sample at the flange opening, drop an iron ball with a diameter of 20 mm and a weight of 33 g through the support tube onto the upper surface of the sample. rice field. The energy of the falling ball was estimated to be 0.32 N·m.
In this way, the fire extinguishing properties and impact resistance of the samples were evaluated. The evaluation criteria were as follows. Table 3 shows the results.
Fire extinguishing property: A rating if extinguishing within 5 seconds after contact with flame, B rating if extinguishing within 5 seconds after contacting flame, C rating if extinguishing could not be extinguished, and
Impact resistance: A rating was given when the shape was maintained, and a B rating was given when the shape was not maintained.

DESCRIPTION OF SYMBOLS 1... Fiber layer, 2... Resin layer, 10... Fire-extinguishing laminate.

Claims (5)

A fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance, and a resin layer,
A fire-extinguishing laminate, wherein at least one of the fiber layer and the resin layer contains a fire-extinguishing agent component that generates an aerosol when burned. The fire-extinguishing laminate according to claim 1, wherein the fiber layer contains at least one selected from the group consisting of carbon fiber, glass fiber, metal fiber and ceramic fiber. The fire-extinguishing laminate according to claim 1 or 2, wherein the fiber layer has a thickness of 0.02 to 2.0 mm. The fire extinguishing according to any one of claims 1 to 3, wherein the resin layer contains at least one selected from the group consisting of urethane resins, epoxy resins, silicone resins, vinyl chloride resins, polyolefin resins, and polyester resins. Laminate for a step of impregnating a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol when burned;
drying the impregnated first liquid composition;
applying a second liquid composition containing a liquid component and a resin onto the fiber layer;
a step of drying the applied second liquid composition;
comprising
A step of applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin onto a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance;
a step of drying the applied third liquid composition;
or
a step of impregnating a fiber layer containing organic fibers or inorganic fibers having high strength and heat resistance with a first liquid composition containing a liquid component and a fire extinguishing agent component that generates an aerosol when burned;
drying the impregnated first liquid composition;
applying a third liquid composition containing a liquid component, a fire extinguishing agent component that generates an aerosol by combustion, and a resin onto the fiber layer;
a step of drying the applied third liquid composition;
A method for manufacturing a fire-extinguishing laminate.

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