JP7787508B2 - Fire-fighting laminate - Google Patents

Description

The present invention relates to a fire-extinguishing laminate.

In recent years, technological advances have made our lives more comfortable, but at the same time, large amounts of energy are required to create that comfort. High levels of safety are required when handling energy in each of the following situations: when large amounts of energy are densely packed and stored, transported, and used.

Taking automobiles as an example, there is a risk of fire when mining fossil fuels, refining gasoline from fossil fuels, transporting gasoline, and burning gasoline in the engine. Taking electronics as an example, there is a similar risk of fire when electrical energy is transferred through power lines, when electrical energy is regulated in substations and transformers, when electrical energy is used in electrical equipment in homes and factories, or when it is temporarily stored in batteries.

To address the problem of ignition and fire, Patent Document 1 proposes the use of fire extinguishing liquid and a fire extinguisher. Patent Document 2 proposes an automatic fire extinguishing device dropped from a helicopter. Patent Document 3 proposes an aerosol fire extinguishing device.

Japanese Patent Application Publication No. 9-276440 Japanese Patent Application Laid-Open No. 2015-6302 JP 2017-080023 A

All of the prior art proposes methods for dealing with fires after a certain amount of time has passed. However, from the perspective of minimizing damage caused by fires, it is desirable to carry out some kind of fire-fighting operation (initial fire extinguishing) shortly after the fire has started.

One possible solution is to place the components of a fire extinguishing agent disclosed in prior art near an object at risk of ignition. This would allow the fire to be extinguished by the components of the fire extinguishing agent before a human can sense the fire starting in the object. However, it is necessary to address the problem of fire extinguishing agents placed in open spaces deteriorating over time. In addition, it is obviously not realistic to simply spray the fire extinguishing agent near the object; it is necessary to place the agent near the object in a form that is reasonably easy to handle.

The present invention was made in consideration of the above circumstances, and aims to provide a fire-extinguishing laminate that is easy to handle, has excellent fire-extinguishing agent property stability, and can prevent the outbreak and spread of fires.

One aspect of the present invention provides a fire extinguishing laminate comprising, in this order: a fire extinguishing agent-containing layer containing a fire extinguishing agent component that generates an aerosol upon combustion and a binder resin; and a resin substrate. With such a fire extinguishing laminate, the resin substrate ensures ease of handling. Furthermore, when the fire extinguishing laminate is placed so that the fire extinguishing agent-containing layer faces an object, the resin substrate functions as a sealant, thereby suppressing deterioration of the fire extinguishing agent. Thus, the fire extinguishing laminate is easy to handle and the properties of the fire extinguishing agent are stable. Furthermore, by placing the fire extinguishing laminate near the object in advance, early fire extinguishing is possible, and the spread of the fire to the surrounding area can be suppressed.

The fire extinguishing agent component contains, for example, at least an inorganic oxidizing agent that burns together with the binder resin to generate thermal energy, and a radical generator, with the radical generator's decomposition starting temperature ranging from 90°C to 260°C. Such a fire extinguishing agent component has excellent fire extinguishing performance. The fire extinguishing agent component contains, for example, at least one of a potassium salt and a sodium salt as the radical generator. Potassium salts and sodium salts have the effect of stabilizing combustion radicals and suppressing the combustion chain reaction (negative catalytic action).

The binder resin content in the fire extinguishing agent-containing layer is preferably 3 to 30% by mass. A binder resin content of 3% by mass or more in the fire extinguishing agent-containing layer ensures excellent coatability.

The thickness of the fire-extinguishing agent-containing layer can be set appropriately depending on the installation location of the fire-extinguishing laminate and the amount of fire-extinguishing agent components to be blended, and can be, for example, 30 to 1,000 μm.

In the fire-extinguishing laminate of the present invention, the resin substrate may contain at least one material selected from the group consisting of polyolefin, polyester, fluororesin, PVC, PVA, acrylic resin, epoxy resin, polyamide, and polyimide.

In the fire-extinguishing laminate of the present invention, the thickness of the resin substrate may be 4.5 to 1000 μm.

In the fire-extinguishing laminate of the present invention, the water vapor permeability of the resin substrate (according to JIS K 7129 under conditions of 40° C./90% RH) may be 2×10 ² g/m ² /day or less.

The fire extinguishing laminate of the present invention may further comprise another resin substrate below the fire extinguishing agent-containing layer. That is, the fire extinguishing laminate of the present invention may comprise another resin substrate, a fire extinguishing agent-containing layer, and a resin substrate in this order. This makes it possible to suppress deterioration of the fire extinguishing agent regardless of the material of the target surface.

The fire-extinguishing laminate of the present invention may further include an adhesive layer between the fire-extinguishing agent-containing layer and the resin substrate, or between the fire-extinguishing agent-containing layer and another resin substrate.

According to the present invention, it is possible to provide a fire extinguishing laminate which is excellent in handleability and stability of the properties of the fire extinguishing agent, and which can prevent the outbreak and spread of fire. The advantages of the present invention are briefly summarized below.
・Damage caused by the spread of fire can be kept to a minimum, meaning that fires can be extinguished in their early stages.
- After a person confirms a fire, there is no need to carry a fire extinguisher to the area where the fire is to be extinguished and carry out firefighting activities.
- Compared to equipment such as automatic fire extinguishing devices, it can be installed more easily, so there are fewer restrictions on where it can be installed and it can be applied wherever necessary.
- The extinguishing agent has excellent stability in properties, which reduces the frequency of replacing the fire extinguishing laminate.

FIG. 1 is a schematic cross-sectional view of a fire extinguishing laminate according to one embodiment. FIG. 2 is a schematic cross-sectional view showing a method of using the fire extinguishing laminate. FIG. 3 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. FIG. 4 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. FIG. 5 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. FIG. 6 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment.

Embodiments of the present invention are described in detail below. However, the present invention is not limited to the following embodiments.

<Fire-extinguishing laminate>
Fig. 1 is a schematic cross-sectional view of a fire extinguishing laminate according to one embodiment. The fire extinguishing laminate 10 includes a fire extinguishing agent-containing layer 1 and a resin substrate 2, in this order. The fire extinguishing laminate may be in the form of a sheet. As shown in Fig. 1, the fire extinguishing agent-containing layer 1 may be provided on at least a portion of the lower surface of the resin substrate 2, but may also be provided on the entire lower surface of the resin substrate 2. In other words, the end faces of the fire extinguishing agent-containing layer 1 and the resin substrate 2 may be flush with each other.

Figure 2 is a schematic cross-sectional view showing how the fire extinguishing laminate is used. As shown in Figure 2, the fire extinguishing laminate 10 is used so that the fire extinguishing agent-containing layer 1 side of the fire extinguishing laminate (or, if the fire extinguishing laminate includes another resin substrate, as described below, the other resin substrate side) faces an object X that may ignite. If a fire breaks out at object X, the pre-installed fire extinguishing laminate will initially extinguish the fire.

Figure 3 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. Fire extinguishing laminate 20 includes another resin substrate 3, a fire extinguishing agent-containing layer 1, and a resin substrate 2, in this order. Figure 4 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. Fire extinguishing laminate 30 includes another resin substrate 3, a fire extinguishing agent-containing layer 1, and a resin substrate 2, in this order, and further includes adhesive layers 4 between the resin substrate 2 and the fire extinguishing agent-containing layer 1, and between the other resin substrate 3 and the fire extinguishing agent-containing layer 1. Figure 5 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. Fire extinguishing laminate 40 includes another resin substrate 3, a fire extinguishing agent-containing layer 1, and a resin substrate 2, in this order, and the peripheries of the resin substrate 2 and the other resin substrate 3 are joined together by a sealing portion 5. Figure 6 is a schematic cross-sectional view of a fire extinguishing laminate according to another embodiment. The fire extinguishing laminate 50 comprises, in this order, another resin substrate 3, an adhesive layer 4, a fire extinguishing agent-containing layer 1, and a resin substrate 2, with the peripheral edges of the resin substrate 2 and the other resin substrate 3 joined together by a sealing portion 5.

The thickness of the fire extinguishing laminate is not necessarily limited because it varies depending on the layer structure, but from the viewpoint of being able to maintain fire extinguishing performance while being thin enough to accommodate a limited installation space, it can be, for example, 0.1 to 20 mm. Furthermore, from the viewpoint of fire extinguishing performance and ease of handling, the area of the main surface of the fire extinguishing laminate (the surface when viewed from above in the vertical direction) can be, for example, 9 to 620 ^cm2 .

(Resin substrate)
The material of the substrate can be a resin substrate. Examples of materials for the resin substrate include polyolefins (LLDPE, LDPE, PP, COP, CPP, etc.), polyesters (PET, etc.), fluororesins (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), PVC, PVA, acrylic resins, epoxy resins, polyamides, and polyimides. Among these, the resin substrate may contain at least one selected from the group consisting of LLDPE, PP, COP, CPP, PET, PTFE, ETFE, EFEP, PFA, FEP, PCTFE, and PVC, from the viewpoint of low water vapor permeability and easy suppression of deterioration of the fire extinguishing agent. Furthermore, selecting a transparent material facilitates visual inspection of the fire extinguishing laminate and confirmation of the replacement period. The resin substrate may also contain a fire extinguishing agent, as described below.

The thickness and breaking strength of the resin substrate can be selected appropriately depending on the amount of heat generated during a fire, the impact, the allowable space, and other factors. For example, a thick resin substrate makes it easier to suppress water vapor transmission, provides strength and rigidity, and allows for a highly flat form, making it easier to handle. Furthermore, a thin resin substrate allows the fire-extinguishing laminate to be installed in a narrow space. The thickness of the resin substrate can be, for example, 4.5 to 1000 μm, or may be 12 to 100 μm, or may be 12 to 50 μm. The resin substrate may also be a laminate of multiple resin substrates.

The resin substrate may be a resin substrate that is heat-resistant and impact-resistant (high-strength, heat-resistant resin substrate). A high-strength, heat-resistant substrate preferably has at least one of a tensile strength of 20 N/cm or more and a melting point of 500°C or more. The resin substrate may contain, as a reinforcing material, materials such as carbon, glass, stainless steel, aluminum, and ceramic, particularly woven fabrics (cloths) made of fibers made from these materials. The resin substrate's heat and impact resistance can prevent holes from being created in the resin substrate due to heat or impact during ignition. This can prevent the fire extinguishing agent from being sprayed in the opposite direction from the target.

The resin substrate has water vapor barrier properties to the extent that the properties of the fire extinguishing agent contained in the fire extinguishing agent-containing layer do not change significantly, regardless of the installation location or usage environment of the fire extinguishing laminate. The water vapor permeability of the resin substrate (under 40°C/90% RH conditions in accordance with JIS K 7129) is not particularly limited because it can be designed depending on the type of fire extinguishing agent, but can be 2 x ¹⁰² g/ ^m2 /day or less, and may be 1 x ¹⁰² g/ ^m2 /day or less. From the viewpoint of adjusting the water vapor permeability, the resin substrate may be provided with a vapor-deposited layer of an inorganic oxide having water vapor barrier properties (alumina vapor-deposited layer or silica vapor-deposited layer).

(Fire extinguishing agent-containing layer)
The fire extinguishing agent-containing layer is a layer containing a fire extinguishing agent component and a binder resin. The fire extinguishing agent component generates an aerosol when burned. The fire extinguishing agent component contains, for example, at least an inorganic oxidizing agent and a radical generator. The radical generator has the effect of stabilizing combustion radicals and suppressing the chain reaction of combustion (negative catalytic action).

The thickness of the fire-extinguishing agent-containing layer can be set appropriately depending on the installation location of the fire-extinguishing laminate and the amount of fire-extinguishing agent components to be blended. The thickness of the fire-extinguishing agent-containing layer may be, for example, 1 mm or less, and may be 30 to 1000 μm, or 150 to 500 μm.

The content of the extinguishing agent component in the extinguishing agent-containing layer (based on the mass of the extinguishing agent-containing layer) is, for example, 70 to 97 mass%, preferably 80 to 95 mass%, and more preferably 85 to 92 mass%. A content of the extinguishing agent component of 70 mass% or more can achieve excellent fire extinguishing performance, while a content of 97 mass% or less can achieve excellent moldability. The amount of the extinguishing agent component per unit area can be set depending on the target to be extinguished. For example, for a small fire such as a cigarette, 25 g/ ^m2 or more is sufficient. For a fire with 1 g of solid fuel, 90 g/ ^m2 or more is sufficient. For a large fire or a large fire such as a fire from a lithium-ion battery, 100 g/ ^m2 or more is preferable.

[Fire extinguishing agent components]
As described above, the fire-extinguishing agent-containing layer contains an inorganic oxidizing agent and a radical generator as fire-extinguishing agent components. These components will be described below.

The inorganic oxidizing agent (hereinafter sometimes referred to as "component (A)") is a component that burns together with the binder resin to generate thermal energy. Examples of inorganic oxidizing agents include potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate, magnesium chlorate, and potassium perchlorate. One of these may be used alone, or two or more may be used in combination.

The radical generator (hereinafter sometimes referred to as "component (B)") is a component that generates aerosols (radicals) using the thermal energy generated by the combustion of the binder resin and inorganic oxidizer. It is preferable to use a radical generator with a decomposition onset temperature in the range of 90 to 260°C. Examples of radical generators include potassium salts and sodium salts. Potassium salts include 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. Examples of sodium salts include sodium acetate, sodium citrate, and sodium bicarbonate. These may be used alone or in combination.

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

Commercially available fire extinguishing agents may be used as the fire extinguishing agent components to be blended into the fire extinguishing agent-containing layer. Examples of commercially available fire extinguishing agent components include K-1 (trade name, manufactured by Yamato Protec Co., Ltd.) and STAT-X (trade name, manufactured by Nippon Koki Co., Ltd.).

[Binder resin]
Thermoplastic resins and thermosetting resins can be used as the binder resin. Examples of the thermoplastic resin include polyolefin resins such as polypropylene resins, polyethylene resins, poly(1-)butene resins, and polypentene resins, polystyrene resins, acrylonitrile-butadiene-styrene resins, methyl methacrylate-butadiene-styrene resins, ethylene-vinyl acetate resins, ethylene-propylene resins, polycarbonate resins, polyphenylene ether resins, acrylic resins, polyamide resins, and polyvinyl chloride resins. Examples of thermosetting resins include rubbers such as 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), multi-vulcanized rubber (T), silicone rubber (Q), fluororubber (FKM, FZ), and urethane rubber (U), as well as polyurethane resins, polyisocyanate resins, polyisocyanurate resins, phenolic resins, and epoxy resins. The binder resin may contain a curing agent component.

Epoxy resins are suitable as binder resins because they are highly compatible with fire extinguishing agent components, soluble in alcohol solvents (described below), and highly stable. Because epoxy resins are highly compatible with potassium salts and sodium salts (radical generators), it is easy to obtain a fire extinguishing agent-containing layer with a uniform thickness. In addition, epoxy resins do not hydrolyze or become embrittled due to moist heat, so fire extinguishing agent-containing layers that use epoxy resins as binder resins have excellent stability. Furthermore, when the fire extinguishing agent-containing layer burns, thermal decomposition begins at approximately 260-350°C, allowing aerosol to be generated without compromising fire extinguishing performance.

It is preferable to use a binder resin having water vapor barrier properties. When a single-layer film made of the binder resin is produced, the binder resin preferably has a water vapor permeability (according to JIS K 7129, under conditions of 40°C/90% RH) of 5 g·mm/m ² /day or less, more preferably 1 g·mm/m ² /day or less. An example of a commercially available binder resin is Maxieve (trade name, manufactured by Mitsubishi Gas Chemical Company, Inc.).

The binder resin content, based on the total amount of the fire-extinguishing agent-containing layer, is, for example, 3 to 30% by mass, preferably 5 to 20% by mass, and more preferably 8 to 15% by mass. A binder resin content of 3% by mass or more can achieve excellent moldability, while a binder resin content of 30% by mass or less can achieve excellent fire-extinguishing performance.

[Other ingredients]
Other components to be blended into the fire extinguishing agent-containing layer include dispersants such as water, solvents, colorants, antioxidants, flame retardants, inorganic fillers, and adhesives. These components may be appropriately selected depending on the composition of the fire extinguishing agent-containing layer and the type of binder resin. The content of other components in the fire extinguishing agent-containing layer (based on the mass of the fire extinguishing agent-containing layer) is, for example, 10 mass% or less.

(Other resin substrates)
As shown in Fig. 3, the fire extinguishing laminate may further include another resin substrate (sealing substrate) below the fire extinguishing agent-containing layer. By using the other resin substrate, the fire extinguishing agent can be more stably retained regardless of the material of the object X.

The other resin substrate may be made of any of the materials exemplified above. When a fire breaks out from object X, or due to heat generated before the fire breaks out, the other resin substrate melts, exposing the fire-extinguishing agent-containing layer. From the standpoint of achieving adequate melting properties and water vapor barrier properties, the other resin substrate is preferably made of polyester (PET, etc.), fluororesin (PTFE, ETFE, EFEP, PFA, FEP, PCTFE, etc.), PVC, etc., but is not necessarily limited to these. The thickness of the other resin substrate may be, for example, 4.5 to 1000 μm, or may be 12 to 100 μm, or may be 12 to 50 μm. The other resin substrate may contain a fire-extinguishing agent.

The other resin substrate has water vapor barrier properties to the extent that the properties of the fire extinguishing agent contained in the fire extinguishing agent-containing layer do not change significantly, regardless of the installation location or usage environment of the fire extinguishing laminate. The water vapor permeability of the other resin substrate (under 40°C/90%RH conditions in accordance with JIS K 7129) is not particularly limited because it can be designed depending on the type of fire extinguishing agent, but can be 2 x ¹⁰² g/ ^m2 /day or less, and may be 1 x ¹⁰² g/ ^m2 /day or less. From the viewpoint of adjusting the water vapor permeability, the other resin substrate may be provided with a vapor-deposited layer (alumina vapor-deposited layer or silica vapor-deposited layer) having water vapor barrier properties.

(Adhesive layer)
As shown in Fig. 4, the fire extinguishing laminate may further include an adhesive layer. In Fig. 4, adhesive layers 4 are shown between the resin substrate 2 and the fire extinguishing agent-containing layer 1 and between the other resin substrate 3 and the fire extinguishing agent-containing layer 1, but the adhesive layer 4 may be provided between the resin substrate 2 and the fire extinguishing agent-containing layer 1 or between the other resin substrate 3 and the fire extinguishing agent-containing layer 1. Also, in the same figure, the other resin substrate 3 and the adhesive layer 4 for adhering it do not necessarily need to be provided. Furthermore, in Fig. 4, the end face of the fire extinguishing agent-containing layer 1 and the end face of the adhesive layer 4 are depicted as being flush with each other, but they do not necessarily need to be flush with each other. For example, the adhesive layer 4 may be provided so as to extend beyond the end face of the fire extinguishing agent-containing layer 1.

By providing an adhesive layer between the resin substrate and the extinguishing agent-containing layer, the extinguishing agent-containing layer can be stably held on the resin substrate. Furthermore, by providing an adhesive layer between another resin substrate and the extinguishing agent-containing layer, it becomes easier to fix the other resin substrate.

The adhesive layer can be selected appropriately depending on the type of resin substrate, other resin substrate, and fire-extinguishing agent-containing layer. The adhesive layer can be formed from materials such as heat-sealing materials, adhesives, and pressure-sensitive adhesives. The thickness of the adhesive layer can be, for example, 1 to 10 μm, and may be 2 to 5 μm.

(Sealing part)
As shown in Figure 5, the fire extinguishing laminate may further include a sealing portion. That is, the fire extinguishing laminate may include a sealing portion that joins the peripheries of the resin substrate and the other resin substrate. By providing the sealing portion, the resin substrate and the other resin substrate are joined, and the fire extinguishing agent is sealed. This prevents the fire extinguishing agent from coming into contact with air, thereby suppressing deterioration of the fire extinguishing performance of the fire extinguishing agent. Furthermore, since the movement of the fire extinguishing agent is hindered by the sealing portion, the fire extinguishing agent can be easily released in the desired direction.

The sealing portion may be formed from a material exemplified for the adhesive layer described above. The peripheral edges of the resin substrate and the other resin substrate may be joined using a material exemplified for the adhesive layer described above. For example, as shown in FIG. 6, when the fire-extinguishing laminate has an adhesive layer between the extinguishing agent-containing layer and the other substrate, the same material can be used to seal the extinguishing agent at the adhesive layer and the sealing portion. The sealing portion may be formed from another UV-curable sealing material. If the resin substrate and/or the other resin substrate itself has heat-sealing properties, the sealing portion may be formed by heat-sealing those substrates. In other words, the sealing portion may be a heat-sealed portion of the resin substrate and/or the other resin substrate. When the sealing portion is a heat-sealing material, the heat-sealing material can be formed on the entire surface of the other resin substrate, and only the outer periphery of the extinguishing agent can be heat-sealed to seal the extinguishing agent. By providing a sealing portion, the extinguishing agent can be sealed without bonding the extinguishing agent to the other substrate.

(Objects that may ignite)
The object is not particularly limited as long as it is flammable and has a surface on which the fire extinguishing laminate can be placed, for example, electric wires, distribution boards, control panels, storage batteries (lithium ion batteries, etc.), building materials such as wallpaper for building materials and ceiling materials, and components of boxes for collecting lithium ion batteries.

As shown in Figure 1, in the case of a fire-extinguishing laminate comprising a fire-extinguishing agent-containing layer and a resin substrate in this order, the surface of the object X is preferably made of a material with low water vapor permeability, such as metal or glass. As shown in Figure 2, in the case of a fire-extinguishing laminate comprising another resin substrate, a fire-extinguishing agent-containing layer, and a resin substrate in this order, the surface of the object X does not necessarily have to be made of a material with low water vapor permeability.

<Method of manufacturing the fire-extinguishing laminate>
As described above, the method for producing the fire-extinguishing laminate is not particularly limited, and the laminate can be produced by appropriately laminating the above-mentioned layers and, if necessary, heat sealing the laminate.

For example, the method for producing the fire-extinguishing laminate shown in Figure 1 includes a step of preparing a coating liquid containing the fire-extinguishing agent component and the binder resin (coating liquid preparation step), a step of forming a coating film on the surface of a resin substrate using the coating liquid (coating step), and a step of drying the coating film to form a fire-extinguishing agent-containing layer on the surface of the resin substrate (drying step).

In the coating liquid preparation process, an alcohol solvent (e.g., ethanol, IPA) is preferably used as the solvent for preparing the coating liquid. Alcohol solvents have excellent dispersibility of fire extinguishing agent components and low volatility, making them suitable as solvents for preparing the coating liquid. Ethyl acetate may also be used as the solvent. The ratio of the amount of solvent to the amount of fire extinguishing agent components and binder resin can be adjusted appropriately depending on the desired viscosity of the coating liquid.

The coating process may be carried out by wet coating or by impregnating the resin substrate with the coating liquid.

The drying process can be carried out by heating the coating to, for example, 50 to 100°C, in order to thoroughly remove the solvent while suppressing the reaction of the fire extinguishing agent components.

Alternatively, the method for producing the fire-extinguishing laminate shown in Figure 1 may include the steps of preparing a fire-extinguishing agent-containing layer formed using the coating liquid, and bonding the resulting fire-extinguishing agent-containing layer to a resin substrate via an adhesive layer.

If the fire-extinguishing laminate includes another resin substrate, another resin substrate with a fire-extinguishing agent-containing layer may be prepared and laminated to the resin substrate.

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

<Preparing materials>
(Substrate and other substrates)
・PVC film: thickness 100 μm
PET film: thickness 50 μm or 100 μm
LLDPE film: thickness 50 μm or 100 μm
・LDPE film: thickness 25 μm
PET film with a vapor-deposited layer of inorganic oxide: thickness 12 μm
・Paper: Thickness 250 μm
(Fire extinguishing agent component)
- Aerosol fire extinguisher (product name: K-1, manufactured by Yamato Protec Co., Ltd.)
(solvent)
・Ethanol (binder resin)
Epoxy resin (product name: Maxieve M-100, manufactured by Mitsubishi Gas Chemical Company, Inc.)
Amine-based epoxy resin curing agent (product name: Maxieve C-93, manufactured by Mitsubishi Gas Chemical Company, Inc.)
(Adhesive layer)
Urethane resin adhesive (product name: Takenate A-525): thickness 5 μm
- Urethane resin adhesive hardener (product name: Takelac A-52)

<Preparation of Laminate>
Example 1
Ethanol was added to the aerosol fire extinguishing agent to prepare a slurry. A binder resin (epoxy resin and epoxy resin curing agent) was added to the obtained slurry to prepare a coating liquid. The mixing ratio of the binder resin to the aerosol fire extinguishing agent was 10:90 by mass (the content of the binder resin based on the total amount of the fire extinguishing agent-containing layer) in the state of the coating film after drying.

The coating solution was applied to a release sheet so that the dry weight of the coating was 475 g/m ² (mass per unit area of the coating film after drying) to form a coating film. This was dried at 90°C for 2 minutes to form a fire extinguishing agent-containing layer with a thickness of 220 μm. A PVC film with an adhesive layer on one side was also prepared. Then, using a laminator, the fire extinguishing agent-containing layer was bonded to the PVC film via the adhesive layer to obtain a laminate.

(Examples 2 and 3, Comparative Example 1)
A laminate was produced in the same manner as in Example 1, except that the materials used were changed as shown in Table 1.

Example 4
The coating solution was applied to a release sheet so that the dry weight of the coating was 475 g/m ² (mass per unit area of the coating film after drying) to form a coating film. This was dried at 90°C for 2 minutes to form a fire extinguishing agent-containing layer with a thickness of 220 μm. Two LLDPE films each having an adhesive layer on one side were also prepared. Then, using a laminator, the fire extinguishing agent-containing layer was bonded to each LLDPE film via the adhesive layer to obtain a laminate.

(Examples 5 to 7, Comparative Example 2)
Laminates were produced in the same manner as in Example 4, except that the materials used were changed as shown in Table 1. In the examples using a PET film provided with a vapor-deposited layer of an inorganic oxide, an adhesive layer was provided on the side of the vapor-deposited layer of the inorganic oxide.

The following evaluations were carried out on each laminate. The results are shown in Table 1.

<Water vapor permeability>
The water vapor permeability of each of the substrates and other substrates was measured. The measurement was carried out in accordance with JIS K 7129 under conditions of 40°C/90% RH. The water vapor permeability was evaluated according to the following criteria.
A: The water vapor permeability was 2×10 g/m ² /day or less.
B: The water vapor permeability was more than 2×10 g/m ² /day and 2×10 ² g/m ² /day or less.
C: The water vapor permeability was more than 2×10 ² g/m ² /day.

<Fire extinguishing agent property stability evaluation>
(Appearance evaluation)
An aluminum foil (50 μm thick) having an adhesive layer on one side was prepared. Then, using a sealer, the laminate of each example was bonded to the aluminum foil via the adhesive layer to prepare a test specimen. For two-layer laminates, the fire extinguishing agent-containing layer side of the laminate was bonded to the aluminum foil. Each test specimen was left for a predetermined number of days under conditions of 40°C/75% RH. The fire extinguishing agent property stability was then evaluated according to the following criteria.
A: The appearance of the laminate did not change even after being left standing for 21 days or more.
B: The appearance of the laminate was not changed after leaving it for 7 days or more but less than 21 days.
C: After being left standing for less than 7 days, there was a change in the appearance of the laminate (discoloration, swelling, etc. of the extinguishing agent-containing layer).

(Corrosion evaluation)
Test specimens were prepared in the same manner as in the appearance evaluation, and left for a predetermined number of days under conditions of 40°C/75% RH, after which the presence or absence of corrosion of the aluminum foil was visually confirmed.

(Total light transmittance measurement)
The total light transmittance was measured excluding the fire extinguishing agent-containing layer using a measuring instrument in accordance with JIS K 7361. The total light transmittance was then evaluated according to the following criteria.
A: The transmittance was 40% or more.
B: The transmittance was less than 40%.

(Visibility)
It was confirmed whether the fire-extinguishing agent-containing layer could be seen through the substrate, and the visibility was evaluated.

The laminate of the example has excellent handleability due to its resin base material, and it was possible to suppress deterioration of the fire extinguishing agent over time. It was also found that when used with metal materials, it is less likely to corrode the metal materials. Furthermore, it has excellent visibility, so it was found that the condition of the fire extinguishing agent-containing layer can be confirmed non-destructively. By placing such a laminate near an object in advance, it is possible to prevent the outbreak and spread of a fire caused by the object igniting.

The fire-extinguishing laminate of the present invention can be particularly suitably used for components used in industrial materials such as building materials, automotive components, aircraft components, and electronics components.

1...fire extinguishing agent-containing layer, 2...resin substrate, 3...other resin substrate (sealing substrate), 4...adhesive layer, 5...sealing portion, 10, 20, 30, 40, 50...fire extinguishing laminate, X...target object.

Claims (9)

a fire-extinguishing agent-containing layer including a fire-extinguishing agent component that generates an aerosol upon combustion and a binder resin;
a resin substrate, in this order ;
The fire-extinguishing laminate , wherein the resin substrate has a water vapor permeability (according to JIS K 7129 under conditions of 40°C/90% RH) of 2 x 102 ^g /m2 ^/ day or less . the fire extinguishing agent component includes at least an inorganic oxidizing agent that burns together with the binder resin to generate thermal energy, and a radical generator;
2. The fire extinguishing laminate according to claim 1, wherein the radical generator has a decomposition starting temperature in the range of 90 to 260°C. The fire-extinguishing laminate according to claim 2, wherein the radical generator is at least one of a potassium salt and a sodium salt. The fire-extinguishing laminate according to any one of claims 1 to 3, wherein the binder resin content is 3 to 30 mass% based on the total amount of the fire-extinguishing agent-containing layer. The fire-extinguishing laminate according to any one of claims 1 to 4, wherein the thickness of the fire-extinguishing agent-containing layer is 30 to 1000 μm. The fire-extinguishing laminate according to any one of claims 1 to 5, wherein the resin substrate comprises at least one selected from the group consisting of polyolefin, polyester, fluororesin, PVC, PVA, acrylic resin, epoxy resin, polyamide, and polyimide. The fire-extinguishing laminate according to any one of claims 1 to 6, wherein the resin substrate has a thickness of 4.5 to 1000 μm. The fire extinguishing laminate according to any one of claims 1 to 7 , further comprising another resin substrate on the opposite side of the fire extinguishing agent-containing layer from the resin substrate. The fire extinguishing laminate according to claim 8 , further comprising an adhesive layer at least one between the extinguishing agent-containing layer and the resin substrate and between the extinguishing agent-containing layer and the other resin substrate.