JP2006061249A - Ashtray having fire extinguishing action, and gel for fire extinguishment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ashtray which has a high fire extinguishing capability, is excellent in sanitary view, and can save labor at the time of cleaning, and in addition, to provide a gel for fire extinguishment having an excellent fire extinguishing action and an excellent deodorizing action. <P>SOLUTION: A specified net-like container for which a refractory material having a smaller specific density than water is bonded is attached to an ashtray. A gel for fire extinguishment containing a specified plant component, or a water-containing gel of a water-absorbent resin having a specified particle size distribution or a water-absorbent resin floating on the water surface is used as the gel for fire extinguishment. In addition, by making the gel for fire extinguishment having the excellent deodorizing action and the excellent fire-extinguishing action exist in the net-like container, the functionalities are increased. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

TECHNICAL FIELD The present invention relates to an ashtray having a net-like container having a fire extinguishing action, an ashtray having a water-absorbing material, and a fire extinguishing gel suitably used as a fire extinguishing material for an ashtray.

Many conventional cigarette ashtrays are structured so that the butts are received in a single container, and in stand-type ashtrays installed at stations and smoking areas in department stores, water is put in to extinguish the fire. Is often seen. In these ashtrays, if the cigarette butt is not sufficiently extinguished, the smoke is already burned and smoke is generated. In addition, even if the cigarette butt fire extinguishes due to fire extinguishing water, it takes time to clean the ashtray separately to dispose of the cigarette butt and water. There are problems and various proposals have been made to solve them.
For example, in Japanese Patent Laid-Open No. 2001-352964 (Patent Document 1), when cleaning a cigarette ashtray, a mixture of butts mixed in an ashtray container and water put for fire extinguishing are simply separated at a time. There has been proposed an ashtray equipped with a sieve that can be cleaned up separately.
JP-A-8-336379 (Patent Document 2) proposes a filter-type ashtray that can easily remove tobacco ash from the particulate deodorant even if the particulate deodorant and cigarette ash are mixed. Yes.
JP-A-6-74 (Patent Document 3) proposes an insole material for an ashtray in which a volatile deodorizing material is supported on a granular base material made of a porous mineral material.
In addition, various proposals have been made to use water-containing gels (hereinafter abbreviated as gels) in which water is absorbed in water-absorbing resins (other names: (high) water-absorbing polymers, water-swellable polymers) as extinguishing materials for ashtrays. ing.
For example, Japanese Patent Application Laid-Open No. 10-192444 (Patent Document 4) has excellent fire extinguishing capability, can maintain the fire extinguishing capability over a long period of time, and can be easily discarded after use. A fire extinguishing gel characterized by containing a substance and water has been proposed.

Japanese Patent Laid-Open No. 2001-9058 (Patent Document 5) proposes a tobacco fire extinguisher characterized by mixing and stirring water, glycol, a water-absorbing acrylic polymer, a porous inorganic substance, and sodium bicarbonate.
Moreover, in Japanese Utility Model Laid-Open No. 7-14898 (Patent Document 6), a gel holding water with a pF value of 3.5 or less is put in an ashtray to extinguish a cigarette in contact with the gel. A gel-containing ashtray has been proposed.
Moreover, in Japanese Utility Model Publication No. 2-39747 (Patent Document 7), an aqueous powder fragrance and a deodorant are mixed in a crystalline superabsorbent resin, and an appropriate amount of water is poured from above the mixed powder at the time of use. A deodorizing fragrance has been proposed in which the resin expands and crystallizes, and the fragrance and deodorization start. At the same time, it is a resin containing water and also serves as a fire extinguisher.
Japanese Patent Application Laid-Open No. 11-69966 (Patent Document 8) proposes a portable ashtray in which a water-absorbing resin layer is provided so that an appropriate amount of water can be held at a required place on the inner surface.
Japanese Patent Laid-Open No. 9-140826 (Patent Document 9) proposes a water additive for water for fire prevention and extinguishing, which includes a water-swellable polymer having a small particle size of less than 2 microns produced by a reverse phase polymerization reaction. In order to adhere well to both the vertical and horizontal surfaces of the combustion product, it has been proposed to use a highly viscous fluid having a viscosity of 500 to 50000 mPa · s.

In addition, in US Pat. No. 5,190,110 (Patent Document 10), an adsorbent crosslinked polymer having a particle size of 20 to 500 microns that is insoluble in water for fire extinguishing is used as a water-miscible medium in order to suppress the loss of water from the combustion product. It has been proposed that the viscosity of the gel solution produced by dispersion should not exceed 100 mPa · s.
Various proposals have been made as described above, but there is room for further improvement in fire extinguishing capacity, deodorizing capacity, ease of cleaning, and fire extinguishing gel used in ashtray fire extinguishing materials. It was.

JP 2001-352964 A JP-A-8-336379 JP-A-6-74 Japanese Patent Laid-Open No. 10-192444 Japanese Patent Laid-Open No. 2001-9058 Japanese Utility Model Publication No. 7-14898 Japanese Utility Model Publication No. 2-39747 Japanese Patent Laid-Open No. 11-69966 JP-A-9-140826 US Pat. No. 5,190,110

If only water is put in the conventional ashtray for fire extinguishing, it takes time and effort to distinguish and throw away the butts and water when cleaning the ashtray, and the nicotine contained in the butts will mix with the water and produce a bad odor and hygiene. There is also a problem. Also, since water evaporates, it is necessary to periodically inject water. Even when using a fire extinguishing gel, in order to maintain a high fire extinguishing capacity over a long period of time, regular water injection work, especially outdoors and in dry environments Is necessary.
In the present invention, an ashtray that can save labor during cleaning, an ashtray that can simplify water injection work for fire extinguishing, an ashtray that has a high fire-extinguishing capability and excellent hygiene, and further has an excellent fire-extinguishing action and deodorizing It aims at providing the gel for fire extinguishing which has an effect | action.

As a result of diligent studies to solve the above problems, the inventors of the present application attached a specific mesh container to an ashtray, a water-absorbing resin having a specific particle size distribution or a water-absorbing resin floating on the water surface. It has been found that it is used as a fire extinguishing material, and further a gel for extinguishing fire having an excellent fire extinguishing action is contained in a mesh container, and the present invention has been completed.
The objects of the present invention are achieved by the following (1) to (21).
(1): A fire-extinguishing gel comprising a water-absorbing resin, a plant component, and water.
(2): The fire extinguishing gel according to (1), further comprising an inorganic salt or an organic salt.
(3) The fire-absorbing gel according to (1) or (2), wherein the water-absorbent resin and the plant component are in a particulate form.
(4) The fire extinguishing gel according to any one of (1) to (3), wherein the plant component is tea leaf and / or tea leaf extract.
(5): Preferably, the tea leaves comprise tea leaves made from green tea, and the proportion of the fine particles of the tea leaves passing through a wire mesh having an opening of 150 μm is 10% by mass or less (4) Gel for fire extinguishing as described in 4.
(6): The ratio of fine particles having a particle diameter of less than 150 μm in the water-absorbent resin before water absorption is 20% by mass or less, for fire extinguishing according to any one of (1) to (5) gel.
(7): A fire-extinguishing gel containing a water-absorbing resin, an inorganic salt or an organic salt, and water, and the proportion of fine particles having a particle diameter of less than 150 μm in the water-absorbing resin before water absorption is 20% by mass or less. A gel for fire fighting.
(8) The fire-absorbing gel according to any one of (1) to (7), wherein the water-absorbent resin is a polyacrylic acid (salt) -based crosslinked polymer.
(9): The fire extinguishing gel according to any one of (1) to (8), wherein the water absorbent resin is preferably spherical particles obtained by reverse phase suspension polymerization.
(10) The fire extinguishing gel according to any one of (1) to (9), wherein the water absorbent resin floats on a water surface.
(11): The fire-extinguishing gel according to any one of (1) to (10), wherein the fire-extinguishing gel is preferably used as a fire extinguishing material for an ashtray.
(12): A fire extinguishing method using the gel for fire extinguishing according to (1) to (11).
(13): The fire extinguishing method according to (12), which is used for extinguishing cigarettes in an ashtray.
(14): A fire extinguishing method characterized by using a water-containing resin hydrogel floating on the water surface.
(15): An ashtray characterized by containing a water-containing resin hydrogel floating on the water surface.
(16): having a water tank (1) storing water, a refractory material (2) having a specific gravity smaller than that of water, and a net-like container (3) containing a cigarette butt, the net-like container (3) An ashtray characterized by floating on the water surface of the aquarium (1) in a state of being joined to the refractory material (2).
(17): The ashtray according to (16), wherein the refractory material (2) is preferably provided on and joined to the upper part of the mesh container (3).
(18): The ashtray according to (16) or (17), wherein the mesh container (3) preferably contains a water-absorbing material (4).
(19) Any one of (16) to (18), wherein the fire-extinguishing gel described in (1) to (11) is floating in the mesh container (3) and is floating on the water surface The ashtray according to one.
(20): The ashtray according to any one of (16) to (19), wherein a material of the mesh container (3) is preferably a stainless steel wire mesh.
(21): The ashtray according to any one of (16) to (20), wherein the ashtray is preferably a stand-type ashtray.

If the ashtray of the present invention is used, the water is constantly in contact with the water just by changing the height of the net-like container floating on the water surface according to the amount of water once it is poured, so the fire extinguishing ability over a long period of time Can be kept high. Moreover, when cleaning the ashtray, it is possible to separate the butts and water by simply lifting the net-like container out of the water tank, so that it is possible to save time and effort to distinguish and throw away the butts. Furthermore, the gel for fire extinguishing of the present invention can easily secure gap water between the gels, and the fire extinguishing action can be improved by the gap water. If the fire-extinguishing gel of the present invention having a high fire-extinguishing capability is contained in the mesh container of the ashtray of the present invention, the functionality is further enhanced.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail based on suitable drawings.
FIG. 1 is a perspective view of a stand-type ashtray according to the first embodiment of the present invention. The appearance is the same as a general stand-type ashtray installed in a smoking area of a station or department store.
2 is an exploded perspective view of FIG. In FIG. 2, the main body of the ashtray has a water tank (1) that stores water, a refractory material (2) having a specific gravity smaller than that of water, and a net-like container (3) that accommodates butts. In this invention, a water tank means the container which can store water. Examples of the material of the container include metal (stainless steel, aluminum), glass, plastic, and the like.
The refractory material (2) preferably has a specific gravity smaller than that of water, and preferably has a specific gravity of 0.02 or more and 0.95 g / cm ³ or less. Specifically, pumice having a specific gravity of 0.5 or more and less than 1.0 g / cm ³ (natural pumice, ceramic pumice), foamed polyethylene covered with aluminum foil, or foamed polystyrene, or a plastic bottle container with a lid, or For example, floating fishing equipment. It may be coated with a metal heat-resistant material other than aluminum. Pumice, which is a volcanic ejecta, has good fire resistance, is a porous non-combustible mineral material, can carry a large amount of aromatic plant essential oil, and foamed polyethylene is preferable in terms of excellent processability. .
Polyethylene foam is a very light material having a specific gravity of 0.025 to 0.20 g / cm ³ . Generally, it is produced by adding an organic foaming agent, a crosslinking agent or the like to low density polyethylene and thermally decomposing the foaming agent and the crosslinking agent in a sealed mold.
Moreover, the plastic bottle container with a lid | cover is preferable at the point which can be used even with a comparatively high load, and the point used as recycling of a waste plastic bottle container.

When these refractory materials with a specific gravity smaller than water are floated on the surface of the water and the mesh container (3) is placed on the surface, the weight of the mesh container (3) must be greater than the buoyancy received from below. For example, the mesh container (3) can maintain a floating state on the water surface. Examples of the material for the mesh container (3) include stainless steel wire mesh and copper wire mesh. The pore size (opening) of the mesh is preferably 1.5 cm or less, more preferably 400 mesh to 3 mesh, further preferably 400 mesh to 16 mesh, further particularly preferably 200 mesh to 20 mesh, and 100 mesh to 60 mesh. Is most preferred. If the mesh opening is larger than 1.5 cm (upper limit), butts and cigarette ash are likely to pass through, and separation work between the butts and water becomes insufficient. If the mesh opening is smaller than 400 mesh (lower limit), the water permeability decreases, so the fire extinguishing capability decreases. The mesh of each wire mesh is 3 mesh (about 6.7 mm), 16 mesh (about 1 mm), 20 mesh (about 850 μm), 60 mesh (about 250 μm), 100 mesh (about 150 μm), 200 mesh (about 75 μm). ), Having an opening of about 400 mesh (about 38 μm). Note that the absolute value of the mesh is based on JIS and Tyler.
In the case of a net-like container that easily rusts, it can be used for a long period of time if the surface is coated with a water-resistant paint. When coating with a paint, 60-100 mesh with a relatively large opening is preferable. If the spread is too small, a portion where the hole is blocked by the paint is generated.

Fire extinguishing water in a conventional stand-type ashtray needs to be poured every time it evaporates. Since the height of the container (3) fluctuates and it is constantly in contact with water, the fire extinguishing ability can be maintained high over a long period of time. Moreover, when the ashtray is cleaned, it can be separated from the water simply by lifting the net-like container from the water tank, so that the labor for distinguishing and throwing away the butts and water can be saved.
When the height of the mesh container changes depending on the amount of water, as a device to keep it horizontal, holes are made in several places in the frame part of the mesh container, and the rod passed through it is fixed to the ashtray body If it does, it will move horizontally along the direction of the bar.
3 is a cross-sectional view of the ashtray body of FIG.
Moreover, other embodiment is shown in FIGS. 4-6 about the joining state of the said mesh container (3) and the said refractory material (2). FIG. 4 floats in a form in which a refractory material is bonded to the bottom of the inside of the mesh container, and FIG. 5 shows a shape of the mesh container having a recess, and the recess serves as a storage space for the butts. In the shape part of the recess, water can be taken in from both below and from the side. FIG. 6 shows a form in which the outer periphery of the concave portion of the mesh container is surrounded by a fire-resistant material and joined. The fire resistant material used in FIG. 6 is preferably a material excellent in workability. For example, foamed polyethylene (surface coating with aluminum foil) can be mentioned.
4 to 6, unlike FIG. 3, the refractory material (2) is characterized in that it is provided and joined to the upper part of the mesh container (3). In this embodiment, even if no load is applied to the mesh container, the weight of the joined refractory material is applied to the mesh container, so that the bottom of the mesh container is sufficiently immersed in water. Because fire extinguishing ability becomes high.
Specifically, this is shown in the comparative experiment of FIG. 8 and FIG. FIG. 7 is a view of each butt receiver as viewed from directly above.
FIG. 8 is a side view of the refractory material (2) floated on a water tank with a butterfly butt that is joined to the upper part of the stainless steel wire mesh (9).
The cigarette storage space for receiving the cigarette wrap enclosed by the aluminum foil-coated foamed polyethylene is sufficiently immersed in water.
FIG. 9 is a side view of the refractory material (2) floated on a water tank with a butterfly butt that is joined to the lower part of the stainless steel wire mesh (9).
The upper part of the stainless steel wire mesh (the butt housing space) that receives the butt can be immersed in water when a load is applied from above. With a 100 mesh wire mesh, the top does not get wet with water unless a load is applied.
From the above comparative experiments, in order to increase the fire extinguishing capability, it is preferable in terms of securing water that the fire resistant material (2) is provided on and joined to the upper part of the stainless wire mesh (9). In addition, the larger the mesh of the stainless wire mesh, the easier it is to immerse in water, but if it is too large, butts and ash fall off, which is not preferable.

FIG. 10 is a cross-sectional view of the ashtray body according to the second embodiment of the present invention. FIG. 10 shows a form characterized in that a water-absorbing material (4) is contained in the mesh container shown in FIG. Specific examples of the water absorbent material (4) include foam materials such as water absorbent resin, HIPE foam, polyurethane foam, tissue, pulp, sponge crushed material, tea leaves, and the like. As an effect of the presence of the water-absorbing material, the water-absorbing material absorbs the water in contact with the bottom outer surface of the mesh container, thereby pulling up water to the bottom inner surface of the mesh container. Since the net-like container floats on the water surface, it can always come into contact with water, and the moisture content of the inherent water-absorbing material can be kept high without decreasing. The water-absorbing material may be any material that exhibits a water-holding power enough to extinguish the fire, but a water-absorbing resin having a large water-holding power is preferable, and a particulate water-absorbing resin is particularly preferable because its effect is increased by capillary action. Moreover, if a water-absorbing resin is contained in the mesh container, mixing of tobacco components such as nicotine into water is suppressed, and turbidity of water is reduced. This is thought to be due to the slow elution of tobacco components into the water due to the presence of a water-absorbing resin that is held by a refractory material having a specific gravity smaller than that of water and floats on the water surface.
In particular, in addition to the form in which the water-absorbent resin floats on the surface of the water while being held by a fire-resistant material with a specific gravity smaller than that of water, the amount of water-absorbent resin used can be reduced by applying a material that can float by itself. There is a possibility.

Other advantages include extinguishing the fire by putting a lit cigarette into the mesh container (3) floating with the buoyancy of the refractory material (2) in the water tank (1), and its butt When the water-absorbing resin is present in the net-like container, the water-absorbing resin in the net-like container can be taken out as a lump of garbage while suppressing the scattering of butts and ash when the net-like container is lifted. In other words, it can be easily disposed as a granulated product by attaching butts and ash. Furthermore, if there is a water-absorbing resin, the possibility of water leakage from the collected garbage bag is reduced.
As described above, the inventor of the present application, as a result of intensive studies on the ashtray, as a result of intensive studies on the ashtray, is excellent in fire extinguishing action for a specific fire extinguishing gel suitably used as an extinguishing material for an ashtray, It has been found that it has a deodorizing action. The details will be described below.
Examples of the water-absorbent resin for obtaining the fire-extinguishing gel of the present invention include a water-swellable crosslinked polymer obtained by polymerizing a hydrophilic monomer, and a water-absorbent resin obtained by crosslinking and polymerizing a water-soluble ethylenically unsaturated monomer. Etc. can be illustrated. Although its structure and composition are not particularly limited, specifically, a partially neutralized crosslinked polyacrylic acid polymer (US Pat. Nos. 4,462,001, 4,654,039, 5,250,640, 5,275,773, etc.), a crosslinked part Neutralized starch-acrylic acid graft polymer (US Pat. No. 4,076,663), isobutylene-maleic acid copolymer (US Pat. No. 4,389,513), saponified vinyl acetate-acrylic acid copolymer (US Pat. No. 4,124,748) No.), hydrolyzate of acrylamide or (co) polymer (US Pat. No. 3,959,569), hydrolyzate of acrylonitrile polymer (US Pat. No. 3,935,099), (meth) acrylamide derivative, vinylpyrrolidone crosslinked polymer, sulfone Acid group-containing crosslinked polymer, N-vinylamide-based crosslinked polymer, ) Acrylic ester cross-linked polymer, starch-acrylic acid crosslinked graft polymers, vinyl alcohol crosslinked polymer, polyalkylene glycol crosslinked polymer, starch-acrylonitrile crosslinked copolymer, and the like.
Among these, a polyacrylic acid (salt) -based crosslinked polymer mainly composed of acrylic acid or a salt thereof excellent in water absorption ability generally used in the field of hygiene is preferable. When the polymerizable monomer for obtaining the polyacrylic acid (salt) -based crosslinked polymer is acrylic acid and / or a salt thereof, the structural unit is 0 to 50 mol% of acrylic acid and 100 to 50 mol of acrylate. % (However, the total amount of both is in the range of 70 to 100 mol% with respect to all structural units), preferably in the range of 10 to 40 mol% of acrylic acid and 90 to 60 mol% of acrylate Those within are more preferred. The ratio of this acid and salt (salt / (acid + salt)) is called the neutralization rate. Examples of the salt include alkali metal salts, ammonium salts, amine salts and the like. In order to form a salt, acrylic acid may be neutralized in the monomer state, acrylic acid and acrylate may be mixed, and polymerization may be performed during or after polymerization of the polymerizable monomer. They may be neutralized as a combination, or they may be used in combination.

The polyacrylic acid (salt) -based crosslinked polymer that is preferably used in the water-absorbing resin of the present invention is used in combination with acrylic acid and / or a salt thereof as a main component, and other monomers are copolymerized as necessary. It may be. Specific examples of other monomers include methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid, 2- (meth) acrylamido-2-methylpropane sulfonic acid, 2- (meth) acryloylethane sulfonic acid, 2 -Anionic unsaturated monomers such as (meth) acryloylpropanesulfonic acid and salts thereof; acrylamide, methacrylamide, N-ethyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) Acrylamide, N, N-dimethyl (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, vinylpyridine Nonionic hydrophilic group-containing unsaturated monomers such as N-vinylpyrrolidone, N-acryloylpiperidine, N-acryloylpyrrolidine; N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate , N, N-dimethylaminopropyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide and cationic unsaturated monomers such as quaternary salts thereof.
In addition, N-alkyl (meth) acrylamide derivatives such as Nn-propylacrylamide, Nn-propylmethacrylamide, N-isopropylacrylamide, N-ethylacrylamide, and N, N-, such as N, N-diethylacrylamide. When a dialkyl (meth) acrylamide derivative, acryloylpiperidine, acryloylpyrrolidine, or the like is used as a main component, the resulting cross-linked polymer exhibits temperature sensitivity. The swollen gel that releases water generates interstitial water between the gels (between the swollen gel particles of the water-absorbent resin and water that is present on the particle surface). May play a role as water.
As a method for introducing a crosslinked structure into the water-absorbent resin of the present invention, a self-crosslinking type that does not use a crosslinking agent, or an internal crosslinking agent having two or more polymerizable unsaturated groups or two or more reactive groups. The thing etc. which copolymerize or react (crosslinkable monomer) can be illustrated.
Specific examples of these internal crosslinking agents include, for example, N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, trimethylolpropane di (meth) acrylate, glycerin tri (meth) acrylate, glycerin acrylate methacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, poly (meth) allyloxyalkane, (poly) ethyl Glycol diglycidyl ether, glycerol diglycidyl ether, ethylene glycol, polyethylene glycol, propylene glycol, glycerol, pentaerythritol, ethylenediamine, polyethyleneimine, and glycidyl (meth) acrylate can be mentioned. Two or more of these internal crosslinking agents may be used. The amount used is 0.002 to 2 mol%, more preferably 0.005 to 2 mol%, and still more preferably 0.01 to 2 mol%, based on the monomer component. When the internal cross-linking agent is less than 0.002 mol%, the proportion of the water-soluble component in the resulting water-absorbent resin increases, and the strength of the water-absorbed gel decreases. On the other hand, if the amount of the internal cross-linking agent exceeds 2 mol%, the cross-linking density becomes too high, the absorption capacity of the resulting water-absorbent resin is lowered, and sufficient water cannot be secured.

In the polymerization, hydrophilic polymers such as starch / cellulose, starch / cellulose derivatives, polyvinyl alcohol, polyacrylic acid (salt), crosslinked polyacrylic acid (salt), hypophosphorous acid, etc. You may add chain transfer agents, such as an acid (salt).
When polymerizing the monomer mainly composed of acrylic acid or a salt thereof in order to obtain the water-absorbent resin of the present invention, bulk polymerization or precipitation polymerization can be performed. In view of ease of control, it is preferable to perform aqueous solution polymerization, reverse phase suspension polymerization, and reverse phase emulsion polymerization using the monomer as an aqueous solution. Such polymerization methods are known in the art and are described, for example, in US Pat. Nos. 4,462,001, 4,769,427 and 4,873,299.

The aqueous solution polymerization is a method in which an aqueous solution of a polymerizable monomer is directly polymerized without using a monomer dispersion solvent such as a hydrophobic dispersion solvent, and can be produced by continuous belt polymerization, continuous or batch kneader polymerization or the like. Reverse phase suspension polymerization or reverse phase emulsion polymerization is a polymerization method in which an aqueous solution of a polymerizable monomer is suspended or emulsified in a hydrophobic organic solvent, and the monomer is dispersed. Examples of the surfactant or dispersant for dispersing the monomer include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
Specifically, examples of the anionic surfactant used include fatty acid sodium such as mixed fatty acid sodium soap and sodium stearate, higher alcohol sodium sulfate, sodium alkyl sulfate, and alkylbenzene sulfonate.
Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene higher alcohol ethers, sorbitan fatty acid esters, and glycerin fatty acid esters.
Examples of cationic surfactants and amphoteric surfactants include alkylamines and alkylbetaines.
Other dispersants include ethyl cellulose and ethyl hydroxyethyl cellulose.

The amount of the surfactant or dispersant used can be appropriately selected depending on the type of polymerization. Generally, it is preferably 0.1 to 30 parts by mass, and preferably 1 to 30 parts by mass with respect to 100 parts by mass of the whole monomer component composed of a polymerizable monomer and a crosslinkable monomer. More preferably, it is 3-5 mass parts more preferably. The amount of these dispersants or surfactants used is 0.001 to 10% by mass, preferably 0.001 to 1% by mass, based on the organic solvent described later.
As the organic solvent used in the reverse phase suspension polymerization or the reverse phase emulsion polymerization, any organic solvent can be used as long as it is basically inert to the polymerization. For example, aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene Etc. Among these, n-hexane, n-heptane, and cyclohexane can be mentioned as preferred solvents from the viewpoint of industrial availability, quality, and the like. These hydrophobic solvents are used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.6 to 5 parts by weight, based on 1 part by weight of the polymerizable monomer-containing aqueous solution. It is.
Examples of the organic solvent used for the reverse emulsion polymerization include methanol, ethanol, isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, and the like. Of these, ethanol and isopropanol are preferred.
In performing the aqueous solution polymerization, reverse phase suspension polymerization or reverse phase emulsion polymerization described above, potassium persulfate, ammonium persulfate, sodium persulfate, t-butyl hydroperoxide, hydrogen peroxide, 2,2'- Radical polymerization initiators such as azobis (2-amidinopropane) dihydrochloride, oil-soluble azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Oil-soluble radical polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile, compounds that generate radicals upon photocleavage such as benzoin ethers, acylphosphine oxides, and acylphosphonates, and 2-hydroxy-2- Radioactivity by hydrogen abstraction or electron transfer of methyl-1-phenyl-propan-1-one, benzophenones, etc. Photopolymerization initiators such as compounds that generate benzene, active energy rays such as ultraviolet rays and electron beams, etc. In addition, oxidative radical polymerization of persulfates such as sodium persulfate and other peroxides When an initiator is used, redox polymerization may be performed by using a reducing agent such as sodium sulfite, sodium hydrogen sulfite, ferrous sulfate, L-ascorbic acid, etc. The optimum polymerization initiator should be selected according to the polymerization method. However, the amount of these polymerization initiators used is usually 0.001 to 2 mol% with respect to the total of the polymerizable monomer and the internal crosslinking agent (crosslinkable monomer) in the monomer, preferably When the amount of these polymerization initiators used is less than 0.001 mol%, the amount of unreacted monomers increases, and thus the resulting water-absorbent resin is obtained. The amount of residual monomer in the On the other hand, when the amount of the polymerization initiator used exceeds 2 mol%, it is difficult to control the polymerization, and the amount of water-soluble components in the resulting water-absorbent resin may increase, which is not preferable.
The temperature at the start of polymerization depends on the type of polymerization initiator used, but is preferably in the range of 15 to 130 ° C, more preferably in the range of 20 to 120 ° C. If the temperature at the start of polymerization or the polymerization temperature during the reaction is out of the above range, the residual monomer amount of the resulting water-absorbent resin will increase, or excessive self-crosslinking reaction will proceed and the water absorption capacity of the water-absorbent resin will increase. May cause inconvenience such as lowering. Further, the reaction time and the polymerization pressure are not particularly limited, and may be set as appropriate according to the kind of the monomer or polymerization initiator, the reaction temperature, and the like.
Thereafter, the hydrogel polymer obtained after the polymerization needs to be pulverized with a meat chopper if necessary, and usually further dried.

In the case of aqueous solution polymerization, the water-containing gel-like polymer obtained during the polymerization reaction or after the completion of the polymerization reaction is about 0.1 mm to about 50 mm, further 0.2 to 10 mm, more preferably 0.5 to When it is broken into pieces of about 5 mm and dried, a water absorbent resin suitable for the present invention can be obtained. Although drying temperature is not specifically limited, For example, what is necessary is just to set it in the range of 100-250 degreeC, More preferably, it is in the range of 120-200 degreeC. The drying time is appropriately determined and is not particularly limited, but is preferably about 10 seconds to 5 hours, and more preferably about 1 minute to 2 hours.
In the case of reverse phase suspension polymerization or reverse phase emulsion polymerization, the hydrogel polymer obtained during or after the completion of the polymerization reaction is solidified by azeotropic dehydration in a state dispersed in an organic solvent such as hydrocarbon. After the amount is adjusted to 60% by mass or more, preferably 70% by mass or more, it can be separated from the organic solvent by decantation or evaporation, and further dried as necessary.
Also, there are various drying methods such as heat drying, hot air drying, vacuum drying, infrared drying, microwave drying, drum dryer drying, dehydration by azeotropic distillation with a hydrophobic organic solvent, and high humidity drying using high temperature steam. This method can be employed and is not particularly limited.
The shape of the water-absorbent resin obtained by the above polymerization is generally an irregular crushed shape, a spherical shape, a fibrous shape, a rod shape, a substantially spherical shape, a flat shape, or the like.

The water-absorbent resin of the present invention may be further subjected to crosslinking treatment with a surface crosslinking agent in the vicinity of the surface. Examples of the surface crosslinking agent that can be used for the surface crosslinking treatment include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4. -Trimethyl-1,3-pentanediol, polypropylene glycol, glycerin, polyglycerin, 2-butene-1,4-diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, , 6-hexanediol, 1,2-cyclohexanedimethanol, 1,2-cyclohexanol, trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene bromide Copolymer, polyhydric alcohol compounds such as pentaerythritol, sorbitol; ethylene glycol diglycidyl ether, polyethylene diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether , Epoxy compounds such as polypropylene glycol diglycidyl ether, glycidol; polyvalent amine compounds such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine, and inorganic or organic salts thereof (for example, Aditinium salts); 2,4-tolylene diisocyanate, hexamethylene diisocyanate, etc. Isocyanate compound; polyvalent oxazoline compound such as 1,2-ethylenebisoxazoline; 1,3-dioxolan-2-one, 4-methyl-1,3-dioxolan-2-one, 4,5-dimethyl-1,3 -Dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolane-2- ON, 1,3-dioxan-2-one, 4-methyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxopan-2- Alkylene carbonate compounds such as ON; oxazolidone compounds such as 2-oxazolidone; epichlorohydrin, epibromohydrin, oxetane compounds, cyclic urea compounds, α-methyl Haloepoxy compounds such as ruepichlorohydrin, and polyvalent amine adducts thereof (for example, Hercules Kaimen; registered trademark); silane couplings such as γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane Agents: Polyhydric metal compounds such as hydroxides or chlorides such as zinc, calcium, magnesium, aluminum, iron and zirconium.
These surface cross-linking agents may be used alone or in combination of two or more. In addition, the usage-amount of the surface crosslinking agent with respect to water absorbent resin is in the range of 0.001-10 mass parts with respect to 100 mass parts of solid content of water absorbent resin, More preferably, it exists in the range of 0.01-5 mass parts. And it is sufficient.
By cross-linking the surface of the water-absorbent resin with the use amount of the cross-linking agent within the above range, the cross-linking density of the surface of the obtained water-absorbent resin can be made higher than that inside the water-absorbent resin, and absorption under pressure A water-absorbing resin having excellent characteristics can be obtained. Further, the initial liquid absorption speed of the water absorbent resin (liquid absorption speed immediately after the start of liquid absorption) is further increased. Moreover, it can reduce that water-absorbing resin coheses with water at the time of mixing with water.
If the amount of the crosslinking agent used is less than 0.001 part by mass, the crosslinking density of the surface of the obtained water absorbent resin cannot be increased more than the inside of the water absorbent resin, and the effect of improving the absorption characteristics under pressure is improved. It may not be obtained sufficiently. On the other hand, when the amount of the crosslinking agent used exceeds 10 parts by mass, the added crosslinking agent is not efficiently used and is uneconomical, and since the crosslinking agent becomes excessive, crosslinking of the surface of the water absorbent resin is performed. Since it becomes difficult to control the density appropriately, the amount of absorption under no pressure may be greatly reduced, which is not preferable.
Water may be used in mixing the surface cross-linking agent of the present invention and the water absorbent resin. The amount of water used is generally more than 0.5 and preferably 10 parts by mass or less, and more preferably in the range of 1 part by mass to 5 parts by mass with respect to 100 parts by mass of the solid content of the water absorbent resin.

Moreover, when mixing a surface crosslinking agent and its aqueous solution, you may use a hydrophilic organic solvent and a 3rd substance. In the case of using a hydrophilic organic solvent, for example, lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol; ketones such as acetone; Ethers such as dioxane, tetrahydrofuran and methoxy (poly) ethylene glycol; Amides such as ε-caprolactam and N, N-dimethylformamide; Sulphoxides such as dimethyl sulfoxide; Ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetra Ethylene glycol, polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, polypropylene Glycol, glycerin, polyglycerin, 2-butene-1,4-diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,2-cyclohexane Examples include dimethanol, 1,2-cyclohexanol, trimethylolpropane, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene-oxypropylene block copolymers, polyhydric alcohols such as pentaerythritol, sorbitol, and the like. The amount of the hydrophilic organic solvent used is preferably 50 parts by mass or less with respect to 100 parts by mass of the solid content of the water-absorbent resin, although it depends on the type, particle size, water content and the like of the water-absorbent resin. A range of 10 parts by mass is more preferable. Further, inorganic acids, organic acids, polyamino acids and the like disclosed in European Patent No. 0668080 may be present as the third substance.
The mixing method for mixing the water-absorbent resin of the present invention and the surface crosslinking agent is not particularly limited. For example, the water-absorbent resin is immersed in a hydrophilic organic solvent and dissolved in water and / or a hydrophilic organic solvent as necessary. Examples thereof include a method of mixing a surface cross-linking agent, a method of directly mixing water and / or a surface cross-linking agent dissolved in a hydrophilic organic solvent by spraying or dropping, and the like.

After mixing the water-absorbent resin and the surface cross-linking agent, a heat treatment is usually performed to carry out a cross-linking reaction. Although the said heat processing temperature is based also on the surface crosslinking agent to be used, 40 to 250 degreeC is preferable. If the treatment temperature is less than 40 ° C, the water absorption characteristics may not be sufficiently improved. When the treatment temperature exceeds 250 ° C., the water absorbent resin may be deteriorated and the performance may be lowered. The heat treatment time is about 1 minute-2 hours, preferably about 5 minutes-1 hour.
In addition, if the surface of the water-absorbent resin is coated with a temperature-sensitive polymer such as an N-alkyl (meth) acrylamide derivative, an acryloylpiperidine, or an acryloylpyrrolidine polymer, a water-absorbent resin whose water absorption capacity varies depending on the temperature is obtained. Therefore, by changing the temperature, the water absorption / release phenomenon occurs, resulting in a polymer whose fire fighting ability changes.
In the present invention, if necessary, insoluble inorganic particles such as SiO ₂ and a hydrophilic solvent, preferably water, may be added and mixed for granulation.
At this time, the amount of water used depends on the water content of the water-absorbing resin to be used, but is usually 0.5 to 20 parts by mass, preferably 0. It is the range of 5-10 mass parts. In the present invention, a hydrophilic organic solvent other than water may be used. It is 0-10 mass parts with respect to 100 mass parts of solid content of a water absorbing resin, Preferably it is 0-5 mass parts, More preferably, it is the range of 0-3 mass parts. The temperature at the time of addition of the hydrophilic solvent is preferably in the range of 0 to 80 ° C., more preferably 40 to 70 ° C. in view of the mixing property. Moreover, the method of spraying or dripping a hydrophilic solvent on water-absorbent resin is preferable, and the method of spraying is more preferable. As for the magnitude | size of the sprayed droplet, 1-300 micrometers of average diameters are preferable, and 1-200 micrometers is more preferable.
Next, the fire extinguishing gel of the present invention (fire fighting hydrous gel) will be described.
The fire-extinguishing gel of the present invention preferably contains 30% by volume or more, more preferably 50% by volume or more, and still more preferably 70% by volume or more of the water-absorbent resin water-swelling gel obtained by the above-described method. Is. As an upper limit, 95 volume% or less is preferable, More preferably, it is 90 volume% or less. Moreover, it is preferable that it is a form of a gel dispersion liquid. The water-swelling gel of the water-absorbent resin has a water absorption amount of 4 times or more, preferably 14 times or more, more preferably 50 times or more with respect to the weight of the water-absorbing resin solid content.
Usually, when the water-swelling gel is allowed to stand, the water-swelling gel dries. However, in the present invention, the water-swollen gel gradually adds water absorbed by adding plant components such as tea leaves and / or tea leaf extract, inorganic salts, and organic salts. Utilizing the release from the gel surface, interstitial water between the gels effective for fire extinguishing (water existing between the swollen gel particles of the water-absorbent resin and water on the particle surface) is generated. That is, when the above additives are added to a water-swollen gel that has absorbed water, the concentration of the extracted component and the salt concentration are improved. In particular, the polyacrylic acid (salt) -based crosslinked polymer has a lower absorption capacity. Water is released. The more water present on the surface of the particles between the water-absorbent resin swelling gel particles, the higher the fire extinguishing ability.
Moreover, the gel for fire extinguishing of this invention has high fire extinguishing ability, and also has high deodorizing ability by including plant components, such as a flavor and a tea leaf. As a preferred method of use, the functionality is further improved when used in a state where water is always supplied from below as in the ashtray of the present invention.

The feature of the gel for fire extinguishing found in the present invention is 1) containing a water-absorbing resin, a plant component and water, and 2) containing a water-absorbing resin, a plant component, water, and further an inorganic salt or an organic salt.
A specific example in which an inorganic salt is added to the fire-extinguishing gel in the water tank (1) is shown in a comparative experiment in FIGS.
FIG. 11 shows a state where a particulate water-absorbing resin is contained in the cigarette housing space of FIG. When a cross-linked polyacrylic acid partially neutralized product is incorporated in the water tank (1) as a water-absorbing resin, for example, polyacrylic acid (Na salt) cross-linked polymer used in paper diapers is 100 to 500 times its own weight. As the water-absorbing resin absorbs a large amount of water and swells, the water-absorbing resin tends to spill out. Since the swollen gel is in direct contact with the atmosphere, the water in the gel gradually evaporates with time and dries. In particular, since the gel surface is easy to dry, the fire extinguishing ability tends to be lowered.
On the other hand, FIG. 12 shows a state when sodium chloride is added to the water tank in the state of FIG. Since sodium chloride, which is an inorganic salt, is added, the salt concentration is increased and the water absorption capacity of the water absorbent resin is decreased, so that the water absorption amount of the swollen gel is decreased. In general, when a water-absorbing resin contains salts in water, the water-absorbing magnification decreases due to the influence thereof. This is because the spread of the polymer chain of the water absorbent resin is suppressed by the presence of salts in water. As a result, the swollen gel shrinks and does not overflow from the butt but becomes a gel dispersion, so that sufficient water between the gels can be secured.
Usually, in various applications in which a water-absorbent resin is used, it is desirable that the water absorption ratio is high. It is necessary to adjust to some extent. As a technique for that purpose, the addition of the inorganic salt has been specifically described above, but the same effect can be obtained with an organic salt or a component extracted from a plant component.

Examples of additives include metal halides of inorganic salts, sulfates, carbonates, hydrogen carbonates, phosphates, metal (nitrite) nitrates, and other metal salts and organic salts in addition to inorganic salts. It is done. These additives may be used alone or in combination of two or more.
Examples of the metal halide include halides such as calcium, magnesium, lithium, zinc, aluminum, potassium, and tin, that is, chlorides, bromides, and iodides of these metals. Sodium chloride can use seawater and is inexpensive. When the deliquescent substances calcium chloride and magnesium chloride are added to the water-absorbent resin, evaporation of water on the surface of the gel is suppressed, and the effect of improving water retention is also exhibited. Incidentally, deliquescence is a phenomenon in which a solid absorbs moisture in the air and gradually dissolves.
The deliquescent substance is water-soluble, and the water vapor pressure of the saturated aqueous solution is lower than the water vapor pressure in the air at the same temperature. Therefore, the deliquescent material is excellent in the ability to suppress the evaporation of water, that is, the water retention capacity. When the deliquescent gel is contained in the fire-extinguishing gel, water retention is improved, and the evaporation of water in the fire-extinguishing gel with time is reduced. That is, the degree to which the fire-extinguishing gel gradually dries with the passage of time decreases, and therefore the fire-extinguishing ability of the fire-extinguishing gel can be maintained over a long period of time.
The metal halide may be an anhydride or may be a hydrate. Compared to monovalent metal salts (sodium chloride, potassium chloride, etc.), divalent metal salts (calcium chloride, magnesium chloride, etc.) can bond polymer chains between the water absorbent resin inside and outside. Inducing and reducing the water absorption capability of the water absorbent resin itself, even if the ion concentration of the external solution is lowered again at the time of disposal of the water absorbent resin, it is less likely to swell further and bulk the waste.
Examples of the sulfate include calcium sulfate, magnesium sulfate, and aluminum sulfate.
Specific examples of the metal (nitrite) nitrate include lithium nitrate, sodium nitrate, calcium nitrate, magnesium nitrate, aluminum nitrate, sodium nitrite, and calcium nitrite.

As the concentration of the inorganic salt or organic salt in the water tank (in the dispersion), the inorganic salt or organic salt may be added in the range of 0.1 to 20% by mass (mass ratio of the inorganic or organic compound mass to water), 0.1-10 mass% is preferable, 0.2-5 mass% is more preferable, 0.3-0.7 mass% is especially preferable.
This will be specifically described as other additives for reducing the water absorption capacity of the water absorbent resin.
Examples of the metal hydroxide include calcium hydroxide and magnesium hydroxide.
Examples of the organic salt include salts of the following compounds used as an ion sequestering agent in JP-A-11-315147.
(1) aminocarboxylic acid and its salt, (2) polycarboxylic acid and its derivative, (3) (poly) phosphoric acid and its derivative, (4) N-acylated glutamic acid and N-acylated aspartic acid and their Salt, (5) β-diketone derivative, (6) tropolone derivative, (7) organophosphate compound.
(1) Examples of aminocarboxylic acids and salts thereof include dihydroxyethyl glycine, iminodiacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, cyclohexane-1, 2-diaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylene glycol diethyl etherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, N-alkyl-N-carboxymethylaspartic acid, N-alkenyl-N′-carboxymethylaspartic acid, and these Alkali metal salt, alkaline earth metal salt, ammonium salt or amine salt. Of these, aminocarboxylic acids having 3 or more carboxyl groups and salts thereof are preferred in terms of sequestering ability.
(2) Examples of polycarboxylic acids and derivatives thereof include succinic acid, polyacrylic acid, citric acid monoalkylamide, citric acid monoalkenylamide, malonic acid monoalkylamide, malonic acid monoalkenylamide, and alkali metal salts thereof. Alkaline earth metal salts, ammonium salts or amine salts are mentioned.
(3) (Poly) phosphoric acid and derivatives thereof include hexametaphosphoric acid, metaphosphoric acid, tripolyphosphoric acid, phosphoric acid alkyl ester, phosphoric acid alkenyl ester and alkali metal salts, alkaline earth metal salts, ammonium salts or amine salts thereof Is mentioned.
(4) Examples of N-acylated glutamic acid, N-acylated aspartic acid and salts thereof include Amisoft HS-11 and GS-11, which are commercially available from Ajinomoto Co., Inc.
(5) Examples of β-diketone derivatives include acetylacetone and benzoylacetone.
(6) Examples of tropolone derivatives include tropolone, β-tyaprisin, and y-tzapricin.
(7) Examples of the organic phosphate compound include ethylidenephosphonic acid; 1-hydroxyethylidene-1,1-diphosphonic acid; aminotrimethylenephosphonic acid; ethylenediaminetetra (methylenephosphonic acid); diethylenetriaminepenta (methylenephosphonic acid). Particularly preferred are 1-hydroxyethylidene-1,1-diphosphonic acid; ethylenediaminetetra (methylenephosphonic acid); diethylenetriaminepenta (methylenephosphonic acid). Preferable examples of the salt include alkali metal salts such as Na salt and K salt, ammonium salt, and amine salt. These compounds are known as a kind of metal sequestering agent.
Among these sequestering agents, aminocarboxylic acids having 3 or more carboxyl groups and salts thereof are preferred, among which diethylenetriaminepentaacetic acid, triethylenetetraaminehexaacetic acid, cyclohexane-1,2-diaminotetraacetic acid, N-hydroxyethyl Ethylenediaminetriacetic acid and its salt are most preferred because they can suppress the deterioration of the gel.
In this invention, the usage-amount of the said ion sequestering agent becomes like this. Preferably it is 0.0001-50 mass parts with respect to 100 weight part of solid content of a water absorbing resin, More preferably, it is the range of 0.0002-10 mass part.

Moreover, the polyvalent metal salt of organic acid is also mentioned. Preferably, it is an organic acid polyvalent metal salt having 7 or more carbon atoms in the molecule, and is composed of a metal salt other than an alkali metal salt such as a fatty acid, a petroleum acid or a polymer acid.
Examples of the organic acid constituting the organic acid polyvalent metal salt include caproic acid, octylic acid, octic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, etc. Examples include fatty acids, benzoic acid, myristic acid, naphthenic acid, naphthoic acid, petroleum acids such as naphthoxyacetic acid, and high molecular acids such as poly (meth) acrylic acid and polysulfonic acid, but organic acids having a carboxyl group in the molecule. Preferably, it is a fatty acid such as caproic acid, octylic acid, octylic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, bovine fatty acid or castor hardened fatty acid. More preferred are fatty acids having no unsaturated bond in the molecule, such as caproic acid, octylic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, and stearic acid. Most preferably, it is a long chain fatty acid having 12 or more carbon atoms in the molecule and having no unsaturated bond in the molecule, such as lauric acid, myristic acid, palmitic acid, and stearic acid. When those having a large number of carbon atoms are added to the water-absorbent resin particles, the surface is subjected to water repellent treatment, and when the water-absorbent resin particles are put into water, a floating phenomenon is observed.
The metal salt constituting the organic acid polyvalent metal salt is not particularly limited as long as it is a metal salt other than an alkali metal salt such as an alkaline earth metal salt or a transition metal salt. Salt, calcium salt, magnesium salt, aluminum salt and zinc salt are preferred. The combination of the organic acid and the metal salt constituting the organic acid polyvalent metal salt is not particularly limited, and these may be used alone and / or in combination of two or more.
The addition amount of the organic acid polyvalent metal salt is preferably in the range of more than 0 and less than 30 parts by mass, more preferably 0.001 parts by mass to 10 parts by mass with respect to 100 parts by mass of the water absorbent resin solid content. .
Next, organic phosphorus compounds, halogen-containing organic phosphorus compounds, inorganic phosphate compounds, and other inorganic compounds such as ammonium bicarbonate used as flameproofing (processing) agents can be mentioned. Considering the toxicity and availability of reagents, inorganic salts of secondary ammonium phosphate or primary ammonium phosphate are actually used in wildfires and also as chemical fertilizers. Since it is a substance, it is practical. Note that the flameproofing process is a process for preventing fire from burning as soon as the flame is approached, and to extinguish as soon as the flame is moved away. These additives are also preferable in terms of salt concentration adjustment and fire prevention.

Next, a plant component is demonstrated. Preferably, the plant powder described in WO03 / 104349 and JP2002-285021 is mentioned.
The plant powder that can be used in the present invention is a vascular plant (seed plant, fern plant), moss plant, algae powder (particulate), preferably a vascular plant powder. Moreover, the thing obtained by grind | pulverizing the plant meal byproduced in the manufacturing process in a plant processing industry or a food processing industry may be sufficient. Furthermore, it is also a preferable form that it is a spice. Moreover, it is also a preferable form that it is a tea leaf and / or a tea leaf extract.
In the present invention, the part used by the plant used as the plant powder particularly satisfies the performance of the present invention (if it can reduce the water absorption capacity of the water-absorbent resin by the extracted component, and has a deodorizing effect). It is not limited. For example, it is at least one portion selected from leaves, branches, stems, stems, roots, fruits, flowers, seeds, bark and the like.
When the plant powder that can be used in the present invention is a vascular plant powder, the vascular plant is preferably a grass family, a maple family, an oyster family, a birch family, an Asteraceae family, a cedar family, a cedar tree. From the family, celery family, rose family, grape family, cypress family, pine family, beech family, cruciferous family, legume family, citrus family, cucurbitaceae family, eggplant family, pepper family, ginger family, camphor family, mallow family, camellia family At least one vascular plant selected. Examples of Gramineae vascular plants include rice, sasa, bamboo, corn, and wheat. Examples of vascular plants belonging to the maple family include maple. Examples of vascular plants belonging to the family Oysteraceae include oysters. Examples of vascular plants belonging to the birch family include anthracnose, hazel, birch, alder, and the like. Examples of the vascular plant belonging to the family Asteraceae include chrysanthemum, burdock, dandelion, mugwort and the like. Examples of the vascular plant belonging to the family Lamiaceae include crabs, sesame seeds, nettles, perillas, and mint. As a vascular plant of the cedar family, for example, cedar, Chinese fir and Thai cedar are listed. Examples of vascular plants belonging to the celery family include bees, carrots, parsley, celery and the like. Examples of the vascular plant of the family Rosaceae include ume, cherry blossom, shimotsuke, rose, apricot, pear, peach, apple, strawberry, plum, hawthorn, loquat, sharinbai, bokeh, kamatsuka, rowan, yamabuki and the like. Examples of vine plants in the vine family include grapes, ivy and wild grapes. Examples of cypress vascular plants include Japanese cypress, Japanese cypress, asunalo, juniper, sawara and the like. Examples of the vascular plant of the Pinaceae family include larch, Tsuga, spruce, pine, fir, cedar and the like. Examples of vascular plants of the beech family include beech, chestnut, cynomolgus, mirakashi, arakashi, and vulgaris. Examples of cruciferous vascular plants include radish and rape. Examples of legume vascular plants include azuki bean, licorice, broad bean and soybean. Examples of citrus vascular plants include mandarin orange, orange, grapefruit, pomelo, salamander, yuzu, lemon, and lime. Examples of cucumber vascular plants include pumpkins, cucumbers, watermelons, loofahs, and dolphins. Examples of solanaceous vascular plants include eggplants, peppers, peppers, and tomatoes. Examples of the vascular plant belonging to the family Pepperaceae include pepper. Examples of the vascular plant of the ginger family include ginger. Examples of the vascular plant belonging to the family Camphoraceae include camphor, camphor, black moji, white moji, bay bay, white duck, and kingfish. Examples of the vascular plant of the mallow family include hollyhock, mallow, fuyo, hibiscus, kanaoi, kenaf and the like. Examples of camellia vascular plants include camellia, hisakaki, sakaki, and mokkoku.
The spices that can be used in the present invention are dried spice seeds, fruits, flower buds, leaves, bark, rhizomes, or used as powders to play the role of food seasoning and seasoning. It is a thing to be made.
Particularly preferred in the present invention are tea leaves and coffee beans and / or extracts thereof. These are preferably crushed particles or powder. An extract refers to an extracted product (extracted component). As the component concentration of the extract (eluate) from these plant components into water increases, the water absorption capacity of the water absorbent resin decreases. For example, the extracted components of tea leaves include amino acids [glutamic acid (Na), theanine, aspartic acid, arginine], catechins [epigallocatechin gallate, epicatechin gallate, epigallocatechin, epicatechin], organic acids [oxalic acid (Na ), Citric acid (Na), succinic acid (Na)], caffeine, sucrose, nucleic acid [guanylic acid (Na), adenylic acid (Na)], inorganic ions [potassium, manganese, phosphoric acid (Na)] There are ingredients. For extraction, an extractant comprising an aqueous solvent system, an organic solvent system, or a mixed solvent system of an aqueous solvent and an organic solvent is used. The extractant shall not be included in the extract.
As tea leaves, for example, agarisuku tea, ashitaba tea, amachazuru tea, aloe tea, ginkgo leaf tea, okogi tea, turmeric tea, vulgar tea, oolong tea, psyllium tea, persimmon leaf tea, licorice tea, chrysanthemum tea, gymnema tea, Cuco tea, Kumazasa tea, Gennoshocha tea, Black tea, Sazaji tea, Perilla tea, Jasmine tea, Sugina tea, Senna tea, Mulberry leaf tea, Buckwheat tea, Tahibo tea, Dandelion tea, Chinese tea, Iron kannon tea, Toka tea, Tochu Tea, Dokdami tea, Nazna tea, Nanten tea, Basella tea, Banaba tea, pearl barley tea, Biwa tea, Puar tea, Matsuba tea, wheat tea, mugwort tea, green tea, hoji tea, gentian tea, rooibos tea, etc. Preferably, it is processed so as to be suitable for drinking from the evergreen shrub of the camellia family and its leaves, and examples thereof include green tea, jasmine tea, black tea, oolong tea and the like. These tea leaves are also preferable in terms of deodorizing and fragrance of cigarette odor due to the aroma components contained.
Green tea includes catechins, caffeine, vitamins (vitamin C, β-carotene, vitamin E), γ-aminobutyric acid, flavonoids, polysaccharides, fluorine, amino acids (theanine), minerals (phosphorus, potassium, Components such as zinc, manganese and selenium).
Even if the same green tea is used as a raw material, the ingredients differ depending on the production method and particle size. For example, roasted tea becomes less caffeine when roasted at high temperatures. When the tea leaves are ultrafine powder, the components are efficiently extracted.
In addition, the above tea leaves include camelliaceae, preferably tea leaves derived from green tea (tea leaves made from green tea), and the particle size of the tea leaves is controlled in order to control the rate of water release from the fire extinguishing gel. Is preferably adjusted. For example, it is preferable to use a material having a small amount of fine particles because the rate of water release becomes slow. When there are many fine particles, the tea leaf component elutes quickly when added to water, and therefore the water absorption ratio is lowered due to the tea leaf component, and the water is immediately released from the fire extinguishing gel. Since the elution rate of the tea leaf component varies depending on the type of tea leaf and the particle size of the tea leaf, it is preferable to increase the proportion of tea leaf fine particles when increasing the water release rate. Furthermore, it is preferable to add a powder obtained by drying the tea leaf extract. Moreover, since the elution of the tea leaf components is accelerated with high-temperature water, it is preferable to use water at room temperature (20 ± 5 ° C.) when the elution rate is slow. Since the elution rate of tea leaves decreases as the number of extractions (uses) increases, the elution rate can be controlled using used tea leaves.

In the tea leaf particle size distribution (dried state: moisture content 5 ± 2%), when the water release rate is slow, the proportion of fine particles is preferably small. For example, fine particles passing through a 100 mesh (mesh opening 150 μm) wire mesh Is 10% by mass or less, preferably 5% by mass or less. Further, it is preferable that the average particle size of the tea leaves is larger than the average particle size of the water-absorbent resin in that water can be released from the fire-extinguishing gel over time.
On the other hand, in order to quickly shrink the fire-extinguishing gel, when the water release rate is increased, the proportion of fine particles is preferably large. For example, the proportion of fine particles passing through a 100 mesh (mesh opening 150 μm) wire mesh is 20 mass. % Or more, preferably 40% by mass or more. In addition, an upper limit is 100 mass% or less, Preferably it is 90 mass% or less.
The amount of tea leaf used varies depending on the type of tea leaf used, but the amount added is preferably 1 to 10000 parts by weight, more preferably 1000 to 9000 parts by weight, based on 100 parts by weight of the water-absorbent resin solid content. preferable. If it exceeds 10,000 parts by mass, the concentration of the tea leaf extract will be high, the absorption capacity of the water-absorbent resin will be remarkably reduced, and the deodorizing effect will not be obtained in accordance with the amount added. Moreover, as a density | concentration with respect to the gel dispersion liquid for fire extinguishing, the range of 0.1-10 mass parts is preferable with respect to 100 mass parts of gel dispersion liquid for fire extinguishing, The range of 0.5-4 mass parts is preferable. Is more preferable.
A form containing only plant components may be used without using a gel. For example, in the case of a fire extinguisher only for tea leaves, if the tea leaves are added in the range of 0.1 to 10% by mass (mass ratio of tea leaf mass to water) as the concentration of tea leaves in the fire extinguishing material (in the tea leaf dispersion) In terms of deodorization, 0.1 to 5% by mass is preferable, and 0.5 to 3% by mass is particularly preferable.
As a method of obtaining a mixture of a plant component such as tea leaves and a water absorbent resin (gel), a method of directly mixing the plant component with the water absorbent resin, or spraying or dropping water on a mixture of the plant component directly with the water absorbent resin A method of mixing, a method of mixing a plant component dispersed in water or a solution of various inorganic salts with a water absorbent resin directly, a method of directly mixing a plant component with a gel obtained by adding water to a water absorbent resin Etc. can be illustrated. It is possible to add a plant component during polymerization of the water-absorbent resin or to directly mix the plant component with the crushed gel after polymerization. However, the water-absorbent resin can be extracted slowly from the plant component. A method in which plant components are directly mixed in a gel to which desired water is added is preferable. In particular, a method of directly mixing plant components at the time of use as a fire extinguishing gel is preferable.

In addition to the additives that can reduce the water absorption capacity of the water-absorbent resin, additives that can impart important aromaticity in the present invention will be described. This additive can exhibit an effect by being added to a water tank, or supported on a non-combustible material such as pumice or a water-absorbing material such as a water-absorbing resin. Specific examples include fragrances, fragrances, deodorizers, and deodorizers, but are preferably water-soluble. In the present invention, fire extinguishing is the primary purpose, so that it is difficult to burn.
For example, since the inorganic salts sodium carbonate, sodium hydrogen carbonate, and sesquicarbonate are weakly alkaline, they can selectively adsorb and deodorize acidic particles that are odor components of tobacco.
As a fragrance | flavor, both a natural fragrance | flavor and a synthetic | combination fragrance | flavor may be sufficient. Natural fragrances include citrus essential oils such as lemon oil, orange oil and lime oil, herbal essential oils such as lavender oil, rosemary oil and peppermint oil, floral essential oils such as rose oil and neroli oil, and other pine and sandalwood oils. Can be mentioned. Synthetic fragrances include alcohol, ester, aldehyde, ketone, phenol, phenol / ether, lactone, and terpene.
When imparting fragrance to a fire-extinguishing gel, a gel or gel dispersion swollen by absorbing a water-soluble fragrance or an aqueous solution containing a fragrance into a water-absorbent resin may be used as a fire extinguishing material. Moreover, you may add a fragrance | flavor and a plant component with deodorizing property to the gel which just absorbed water later.
As the water-absorbing resin for obtaining the above-mentioned fire-extinguishing gel, various known water-absorbing resins can be employed, and are not particularly limited. From the viewpoint of easily releasing water (releasing water from a gel that has absorbed a lot of water to enhance the fire-extinguishing action), a polyacrylic acid (salt) -based crosslinked polymer is preferable, and the viewpoint of maintaining water absorption even when the salt concentration is high In the case of (the fluctuation of the water absorption ratio due to the salt concentration is small), a crosslinked polymer having excellent salt resistance is preferable. In any case, it is preferably particulate. The spherical shape, preferably the spherical particle shape, improves the fluidity of the gel dispersion and improves handling, and when a lit cigarette is thrown in, it tends to sink below the gel layer and extinguishes fire. Increases performance.
Polyacrylic acid (salt) -based crosslinked polymers have a very high ability to absorb water, and it is likely that sufficient water between the gels cannot be secured, so the addition of the inorganic salts and organic salts described above and It is necessary to control the particle size distribution described.
Furthermore, another feature of the fire-extinguishing gel found in the present invention is 3) a fire-extinguishing gel containing a water-absorbing resin, an inorganic salt or an organic salt, and water, and the particle diameter in the water-absorbing resin before water absorption The proportion of fine particles less than 150 μm is 20% by mass or less, and the particle size distribution of the water absorbent resin before water absorption (before mixing with water, solid content 95 ± 3%) It is preferable that there are few fine particles. For example, the weight average particle diameter of the water absorbent resin before water absorption is preferably 120 μm or more and 5 mm or less, more preferably 150 μm or more and 3 mm or less, particularly preferably 150 μm or more and 850 μm or less, and most preferably 150 μm or more and 250 μm or less. . The proportion of fine particles having a particle diameter of less than 150 μm is 30% by mass or less, preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 5% by mass or less, and most preferably 1% by mass or less. The proportion of fine particles having a particle diameter of less than 75 μm is 20% by mass or less, preferably 15% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less. The proportion of fine particles having a particle diameter of less than 45 μm is 5% by mass or less, preferably 3% by mass or less, and most preferably 1% by mass or less.
The “particles of 150 μm or more” as used in the present invention are classified on a standard sieve (JIS or equivalent, ASTM, Tyler) having a 150 μm opening measured after classification by the sieve classification method described later. Refers to particles. Similarly, “particles of less than 150 μm” refer to particles that have been classified by a classification method described later and passed through a mesh having a 150 μm mesh measured. The same applies to the sizes of the other openings. Further, when 50% by weight of the particles are classified with a mesh having an opening of 150 μm, the weight average particle diameter (D50) is 150 μm.
If there are many fine particles, the water gap between the gels when water is absorbed (between the swollen gel particles of the water-absorbent resin, the water existing on the particle surface) decreases, so the efficiency of fire extinguishing decreases. In addition, since the fluidity of the gel dispersion liquid is reduced, when the gel dispersion liquid is sent by a pump, the gel dispersion liquid may be difficult to use, such as being clogged due to adhesion to the apparatus.

In the fire-extinguishing gel characterized by 1) containing a water-absorbing resin, a plant component and water, and 2) containing a water-absorbing resin, a plant component, water, and an inorganic salt or an organic salt. Since the fire extinguishing performance is further improved by reducing the fine particles of the water absorbent resin, it is preferable to adjust the particle size distribution as described above.
The following numerical range is mentioned for the suitable ratio of each component in the gel for fire extinguishing of this invention.
First, the mass ratio when water-absorbing resin, plant component and water are included as essential components is, for example,
The numerical range of water-absorbing resin (0.05 to 20% by mass), plant component <preferably tea leaf and / or tea leaf extract> (0.3 to 20% by mass), water (60 to 99.5% by mass). Can be mentioned.
The mass ratio when water-absorbing resin, plant component, water, and inorganic salt or organic salt are included as essential components is, for example, water-absorbing resin (0.05 to 20% by mass), plant component <preferably tea leaf and / or tea leaf. The numerical value range of extract> (0.3-10 mass%), water (50-99.5 mass%), inorganic salt or organic salt (0.05-30 mass%) is mentioned.
The mass ratio when water-absorbing resin and inorganic salt or organic salt and water are included as essential components is, for example, water-absorbing resin (0.05 to 20% by mass), inorganic salt or organic salt (0.05 to 30% by mass). ) And water (55 to 99.5% by mass).
The total amount of each component is preferably 90% by mass or more, and more preferably 95% by mass or more, with respect to the total amount of each fire-extinguishing gel.
In addition to the above components, other components such as water-insoluble inorganic fine particles, water-soluble polymers, and surfactants can be mixed within the range that does not impair the fire extinguishing performance and deodorizing performance of the fire extinguishing gel. . The ratio of the other components is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the fire-extinguishing gel (composition).
In particular, examples of the water-soluble polymer include polyethylene glycol, sodium carboxymethyl cellulose, protein degradation products, and the like, which have an effect of increasing the functionality of the fire extinguishing material (reducing the coefficient of friction of water, increasing viscosity, stabilizing foam).
The particle size adjustment may be adjusted at the time of carrying out dispersion polymerization in the form of particles as in reverse phase suspension polymerization. However, in the case of aqueous solution polymerization, it is usually adjusted to a specific particle size by pulverization and classification after drying.
The water absorbent resin obtained in the present invention has an absorption capacity under no pressure (absorption capacity for 30 minutes under no pressure with respect to a 0.90 mass% sodium chloride aqueous solution) of 10 g / g or more, more preferably 20 g / g or more. More preferably, it is 30 g / g or more, and particularly preferably 40 g / g or more. The absorption ratio may be controlled by controlling the aforementioned polymerization conditions and drying conditions such as an internal crosslinking agent, and the upper limit can be increased to 60 g / g.
Further, the soluble component (also referred to as water-soluble component) that is a soluble component in water or an aqueous solution is preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 15% in the water-absorbent resin. It is below mass%. The lower limit of the soluble content can be reduced to 1% by mass by the production method.

Next, a method for producing a fire-extinguishing gel, that is, a method for mixing a water-absorbing resin, a plant component <preferably tea leaf and / or tea leaf extract>, water, and an inorganic salt or an organic salt is not particularly limited. Various methods can be employed. Specifically, for example, a method of adding a plant component, an inorganic salt or an organic salt to a gel in which water is absorbed in a water-absorbent resin; all of the water-absorbent resin, plant component, water, and an inorganic salt or an organic salt at a time Method of mixing; Method of mixing water-absorbing resin, inorganic salt or organic salt, and water, then mixing plant component; Mixing water-absorbing resin, plant component, inorganic salt or organic salt, and then adding water A method of mixing; a method of mixing an aqueous solution of an inorganic salt or an organic salt after mixing a water absorbent resin and a plant component; a mixture of a plant component and an inorganic salt or an organic salt and water prepared in advance in the water absorbent resin Method of mixing; Method of mixing a mixture of water-absorbing resin, plant component and inorganic salt or organic salt prepared in water; Method of adding water-absorbing resin and plant component to aqueous solution of inorganic salt or organic salt And the like. The fire-extinguishing gel may contain a water-absorbing resin, a plant component, water, an inorganic salt or an organic salt, and the water-absorbing resin may be in a gel or gel dispersion, but as a fire extinguishing gel for an ashtray It is preferable that the release of water and deodorization are exhibited gradually after the plant component, inorganic salt, or organic salt is added to the gel that has first absorbed a large amount of water.
The amount of water used for the water-absorbent resin, that is, the water content (moisture content) that the fire-extinguishing gel should contain is the composition of the water-absorbing resin, the type of inorganic salt or organic salt, and combinations thereof; What is necessary is just to set suitably according to a use etc., Although it does not specifically limit, The more, the more excellent the fire extinguishing ability. For example, the pure water containing no inorganic salt or organic salt is absorbed 30 times or more, preferably 50 times or more, more preferably 60 times or more, particularly preferably 80 times or more, and sufficient water is stored for release. A fire extinguishing gel is preferred. An upper limit of 300 times is sufficient.
Especially in the case of a combination of salt-resistant water-absorbing resin ((meth) acrylic ester-based cross-linked polymer, polyalkylene glycol cross-linked polymer, etc.) and a deliquescent material, the water-absorbing resin is a deliquescent material at the time of manufacture of the gel And swell and gel by containing water to retain the deliquescent material and water. The deliquescent material absorbs water vapor in the air, and the water absorbent resin retains water. Therefore, the gelled water absorbent resin absorbs water vapor in the air so that the water vapor pressure in the air and the water vapor pressure generated by the water in the water absorbent resin maintain a certain balance, Alternatively, water in the water absorbent resin is evaporated. That is, the fire-extinguishing gel can maintain a stable water-containing state for a long period of time, although the water content slightly varies with changes in temperature (air temperature) and relative humidity.
For example, the salt-resistant water-absorbing resin is a crosslinked polymer obtained by polymerizing a monomer component containing a (meth) acrylic acid ester monomer disclosed in JP-A-10-192444. Preferably, the liquid absorption ratio with respect to the saturated calcium chloride aqueous solution is 5 g / g or more. More preferably, the deliquescent material is calcium chloride.
As a fire extinguishing method using the fire extinguishing gel (dispersion liquid) of the present invention, the fire extinguishing gel (dispersion liquid) may be brought into contact with a combustion product or an ignited product, and the contact time is lengthened, and a sufficient amount is sufficient. The fire-extinguishing efficiency can be increased by covering the combustion products with a fire-extinguishing gel (dispersed liquid) and blocking the air from the air. Specifically, there are a method of discharging a fire extinguishing gel (dispersion) toward a combustion product or an igniting product and a method of introducing an igniting product into the fire extinguishing gel (dispersion). For example, since the ignited material includes a lit cigarette, it is suitably used as a fire extinguishing material for an ashtray. In particular, it is preferable to reside in the specific ashtray of the present invention. In addition, the application of a fire extinguishing gel in a fire extinguisher bucket or the like (preferably contained in a specific net-like container joined with a refractory material having a specific gravity smaller than water in view of separation from water) is also conceivable. For example, it is also suitably used as a fire extinguishing material for general fires such as building fires and forest fires. When using water for fire fighting activities, there is a problem that the time required for fire extinguishing becomes longer due to the loss of water or the amount of water used increases, but there is a possibility that it can be improved by adding a water absorbent resin to the digestive juice . Various reports have been made so far. For example, the following fire extinguishing method can be considered when the mechanism of the present invention is used.
After sprinkling a fire extinguisher containing water-absorbing resin and inorganic salt to the fire site with a hose, and spraying water-only fire-extinguishing liquid, water with low salt concentration will be applied to the water-absorbing resin later, so that the water-absorbing resin further absorbs water. As the degree of swelling increases, there is a possibility that water loss can be suppressed. The degree of swelling of the water-absorbent resin can be adjusted by changing the salt concentration, such as using a hose that sprays only water. Also, it is difficult to recover the swollen gel for fire extinguishing scattered at the fire site after the fire fighting is over, so the high concentration fire extinguisher containing divalent metal salt (calcium chloride, magnesium chloride, etc.) Sprinkling water induces bonds between polymer chains inside and outside the water-absorbent resin and reduces the water-absorbing ability of the water-absorbent resin itself, so that the swollen gel can be shrunk. Compared to a monovalent metal salt, it is preferable in that it is less likely to swell even if the concentration of the inorganic salt is lowered again.
As described above, the method for using the fire-extinguishing gel by adjusting the concentration of the inorganic salt has been described, but by adjusting the degree of swelling of the swollen gel and the amount of gel between the gels by the extraction component by adding the plant component <preferably tea leaf and / or tea leaf extract> The adhesiveness can be reduced. For example, if the powder of tea leaves or tea leaf extract is sprayed after completion of the fire fighting activity, the swelling gel used for fire fighting can be contracted. However, inorganic salts are preferred because they are effective when added in small amounts.
It should be noted that a fire extinguishing pump or hose by agglomeration of gel particles by adjusting the water absorbent resin to a specific particle size distribution with a small proportion of fine particles as in the present invention and adding plant components, inorganic salts or organic salts It is also conceivable that blockage of a device such as a nozzle can be suppressed.

The inventor of the present application further examined the present invention from another point of view, and was able to find out the characteristics and effects of the water-absorbing resin floating in water or floating on the water surface. Speaking of features, a fire extinguishing gel characterized in that the water absorbent resin described above floats on the water surface, a fire extinguishing method characterized by using a water-containing gel of a water absorbent resin floating on the water surface, An ashtray characterized by containing a hydrous gel of a floating water absorbent resin.
In the present invention, it has been described that the water-absorbent resin floats on the water surface by being held by an object having a specific gravity smaller than that of water. However, there are some that float on the water surface or float on the water surface only with the water-absorbent resin.
For example, a water-swellable crosslinked granular polymer having a porous structure described in JP-A-9-507085 and having a density of less than 1.0 g / cm ³ in a swollen state, and the surface described in Japanese Patent Application No. 2004-032489 is repellent. Water-treated water-absorbing resin is mentioned. Preferably, the polymer has a porous structure and has a low specific gravity. When a fire is extinguished, the polymer and water slurry can be well sprayed or pumped to effectively extinguish the fire.

In the present invention, the water absorbent resin is floated on the water surface by being held by an object having a specific gravity smaller than that of water. Examples include pumice (natural pumice, ceramic pumice), foamed polyethylene (polyethylene foam) with aluminum foil covered on the surface, and the like. As a method of floating on the water surface, there is a method of combining a water-absorbent resin with an object (for example, crushed material) having a specific gravity smaller than that of water, in addition to a method of placing on an object having a specific gravity smaller than that of water. For example, a method in which an object having a specific gravity smaller than that of water is dispersed in a polymerization vessel at the time of polymerization of a water-absorbent resin, and a method in which a granulated product is obtained after polymerization are exemplified. That is, the water-absorbent resin contains an object having a specific gravity smaller than that of water. So far, a method of containing bubbles, a method of containing cork powder, etc. are known, but in the present invention, the water absorbent resin is floated on the water surface by another method, and further, the water absorbent resin floating on the water surface is removed. We were able to find out how to apply to fire extinguishing materials and how to extinguish them using the digestive materials.
Examples of the object having a specific gravity smaller than that of water include foam materials such as polyurethane foam, cellulose sponge, melamine foam, and HIPE foam described in Japanese Patent Application No. 2003-144421. In particular, the HIPE foam has an average diameter of 0.5 to 100 μm, a small pore diameter, a dry density of 0.1 g / cm ³ or less, and continuous pores having a pore volume of 9 cm ³ / g or more. The average diameter of the flexible polyurethane foam is 100 to 1000 [mu] m, dried density 0.01~0.03g / cm ^3, a melamine foam average diameter 800μm or less, dry density can be applied is of about 0.01 g / cm ^3.
When a foam material with high water absorption is floated on water, the water penetrates into the upper surface of the foam material and becomes sufficiently wet. Even in a form in which natural pumice is floated and these foam materials are placed on the top, the foam material absorbs water and the upper surface becomes wet. When a water-absorbing resin is placed on the upper surface, the water-containing gel retains sufficient water so that the fire extinguishing ability is enhanced.
Specifically, the water-absorbing resin floats on the water surface in the state of FIG. 13 where the water-absorbent resin is held on the natural pumice and floats in the water tank, and the water-absorbent resin is held on the HIPE foam and floats on the water tank in FIG. There are forms. In these forms, it is necessary to float with sufficient water. In particular, when the amount of water retained in the foam material is small, the surface is easy to dry, so the fire extinguishing ability is significantly reduced.

In the present invention, the HIPE foam means a porous polymer having open cells obtained by polymerizing a water-in-oil type highly dispersed phase emulsion. More specifically, a water-in-oil type high dispersion phase emulsion is expressed in English as Water in Oil type High Internal Phase Emulsion (HIPE). A porous polymer (HIPE foam) having an open cell (abbreviated as open cell) can be obtained. Some HIPE foams retain a compressed body when compressed and dried, while others return to an expanded body when compression is released. This depends on the pore size, the W / O ratio, and the elasticity of the polymer.
HIPE is an emulsion with a ratio (W / O ratio) of the water phase that is the dispersed phase (inner phase) and the oil phase that is the outer phase (W / O ratio) of about 3/1 or more. This HIPE is polymerized to form a porous polymer. It is known to manufacture (Japanese Patent Laid-Open No. 57-198713, Japanese Patent Laid-Open No. 2002-20408, etc.). A porous polymer (foam) produced using a foaming agent without being made into HIPE produces a porous polymer from HIPE, compared to a foam with a relatively large pore size that is easy to obtain. The method (HIPE method) is excellent as a method for producing low-density foam having open pores with fine pores. Among the known HIPE foams used in the present invention, the water absorption ratio is 25 (g / g) or more, preferably 35 (g / g) or more, more preferably 50 (g / g) or more, and it is compressed in the longitudinal direction. Those are preferred. (It has a very high absorption / expansion performance in the direction of compression at the time of production.) The polymerizable monomer, the crosslinkable monomer, the surfactant, and the polymerization initiator, which are raw materials for HIPE foam, are disclosed in JP-A-2002. What is illustrated by 20408 can be used.
Production examples of preferred HIPE foam in the present invention (Examples 1 and 2 of JP-A No. 2002-20408) are shown below.
(Production Example 1)
5.1 parts by mass of 2-ethylhexyl acrylate (hereinafter, simply referred to as “parts”), 3.1 parts of 42% divinylbenzene (other component is p-ethyl-vinylbenzene), 1,6-hexanediol diacrylate A monomer component consisting of 1 part, 0.6 part of glycerin monooleate as a surfactant and 0.1 part by weight of ditallowdimethylammonium methyl sulfate were added and dissolved uniformly to obtain an oil phase mixture solution (hereinafter referred to as (Referred to as “oil phase”). On the other hand, 18 parts of calcium chloride was dissolved in 425 parts of ion-exchanged water to prepare an aqueous phase aqueous solution (hereinafter referred to as “aqueous phase”) and heated to 85 ° C. The oil phase and the aqueous phase were continuously fed into the stirring mixer at the above ratio to continuously form a water-in-oil type highly dispersed emulsion (HIPE). The ratio of the water phase to the oil phase was 44.3 / 1, and the HIPE formation temperature To was 85 ° C.

  The obtained HIPE was continuously extracted from the stirring mixer, heated to 85 ° C. in advance, and supplied to a static mixer equipped with a heating and heat retaining member. Separately, 0.5 parts of sodium persulfate as a water-soluble polymerization initiator dissolved in 6 parts of ion-exchanged water was fed from the entrance of the static mixer, and HIPE and the polymerization initiator were continuously mixed. As a result, the ratio of the water phase to the oil phase finally became 45/1.

This HIPE was conveyed through a heat-insulated and heated flexible tube, and was cast into a stainless steel square polymerization container having a length of 1100 mm, a width of 100 mm, and a thickness of 5 mm, which had been kept warm at 85 ° C. in advance. Shaping temperature T ₁ of the HIPE was 81 ° C.. The upper pig was placed and immersed in a water bath having a polymerization temperature T _{2 of} HIPE of 85 ° C. The container was pulled up 15 minutes after the start of heating to obtain a cured water-containing porous polymer. The amount of the polymerization initiator that finished decomposing in 15 minutes was determined to be 0.314 mol%. The porous polymer (HIPE foam) was obtained by dehydrating and compressing the porous polymer.
(Production Example 2)
The same HIPE containing the polymerization initiator (formation temperature To = 85 ° C.) as that obtained in Production Example 1 was conveyed through a heated and heated flexible tube, heated to 85 ° C. and installed horizontally. On a belt running at a constant speed, it was continuously formed into a sheet having a width of about 50 cm and a thickness of about 5 mm. Shaping temperature T ₁ of the HIPE was 82 ° C.. This HIPE was continuously polymerized by passing through a polymerization zone in which the polymerization temperature T ₂ was controlled to 85 ° C. in about 15 minutes to obtain a cured water-containing porous polymer. The amount of the polymerization initiator that finished decomposing in 15 minutes was determined to be 0.314 mol%. The porous polymer (HIPE foam) was obtained by dehydrating and compressing the porous polymer.

As described above, the water-absorbent resin can be floated on the water surface by being held in various materials. Since it is always in contact with water in the floating state, a sufficient amount of water can be maintained.
Floating water-absorbing resin in water or floating on the water surface enables efficient fire extinguishing with a small amount of water-absorbing resin, control of water evaporation rate by floating on the water surface (amount of gel), cigarette components in ashtray Can reduce the odor and water stains, facilitate the collection of gels and butts, increase the deodorizing effect when present on the surface, and add a colorant to the gel to improve its appearance. There are effects such as cleansing. In particular, when floating in water containing fragrance components, the gel is held on the surface of the gel alone or an object having a specific gravity smaller than that of the water. Long lasting.
As for the fire extinguishing method, as described above, the fire-extinguishing gel that can float in the water or float on the water surface may be brought into contact with the combustion product or the ignited material. By floating on the water surface, in extinguishing cigarettes in an ashtray, there is a possibility that the amount of water-absorbing resin used can be reduced, and the practicality can be enhanced by increasing the deodorizing effect.

Hereinafter, although an example of an experiment (an example and a comparative example) explains the present invention still in detail, the present invention is not limited to these. Unless otherwise specified, “part” in Examples and Comparative Examples indicates “part by mass”, and “%” indicates “% by mass”. In addition, mass thru | or mass% and weight thru | or weight% are handled as a synonym.
When measuring the physical properties of the water-absorbent resin in the present invention, if water is absorbed or absorbed, the water content of the water-absorbent resin is balanced (5 to 60 ° C for about 16 hours) as appropriate. Measured after drying to ± 3% by mass).
It describes about the water-absorbing resin used below, the component of tea leaves, etc.
(I) Fragrance gel 1 (component; including water, fragrance, water absorbent resin, amphoteric ion exchanger)
(II) Fragrance gel 2 (Ingredients; including perfume, water-absorbing resin, biodeodorant antibacterial agent)
(III) Water-absorbing resin 3 (surface crosslinked product)
(IV) Water-absorbing resin 4 (surface-crosslinked product)
(V) Water-absorbent resin 5 (mainly uncrosslinked product)
(VI) Jasmine tea leaves (VII) Hojicha tea leaves (VIII) Green tea powder (dried tea leaf extract)
The particle diameters of the aromatic gel 1 and the aromatic gel 2 are shown below.
Particle diameter before water absorption: 100 mesh (aperture 150 μm) -ON is contained by 99% by mass or more. That is, the proportion of fine particles passing through a 100 mesh (mesh 150 μm) wire mesh is 1% by mass or less. All are spherical particles with very few fine particles.
It shows below about the manufacturing method of the water absorbing resin 3-5.

(Production Example 3) Production Method of Water Absorbent Resin 3 21.6 parts of acrylic acid and 228.6 parts of 37 mass% aqueous solution of sodium acrylate, 0.0056 parts of N, N′-methylenebisacrylamide (0.003 parts of monomer) Mol%), 0.106 parts of hydroxyethyl cellulose and 53 parts of ion-exchanged water were used to obtain a monomer aqueous solution having a monomer concentration of 35% and a neutralization rate of 75%. Was dissolved and nitrogen gas was blown to drive out dissolved oxygen.
In a four-necked separable flask equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube and dropping funnel, 800 parts of cyclohexane is added, and 4 parts of sucrose fatty acid ester (HLB = 6) is added as a dispersant. It was dissolved and nitrogen gas was blown to drive out dissolved oxygen. Next, the monomer aqueous solution was added to the above separable flask with stirring and dispersed. Thereafter, the bath temperature was raised to 65 ° C. to initiate the polymerization reaction, and then held at this temperature for 2 hours to complete the polymerization. After the completion of the polymerization, most of the water was removed by azeotropic dehydration, followed by filtration and drying under reduced pressure at 100 ° C. to a constant weight to obtain a water-absorbing resin having a spherical shape with a water content of 8%. 100 parts of the resulting water-absorbent resin was mixed with 0.1 part of ethylene glycol diglycidyl ether, 3 parts of water, and 1 part of isopropanol. The resulting mixture was heated at 120 ° C. for 30 minutes, and then the particles were mixed with methanol. The water-absorbent resin 3 was obtained by processing.
(Production Example 4) Production Method of Water Absorbent Resin 4 21.6 parts of acrylic acid and 228.6 parts of 37 mass% aqueous solution of sodium acrylate, 0.0148 parts of N, N'-methylenebisacrylamide (0.008 monomer) Mol%), 0.106 parts of hydroxyethyl cellulose and 53 parts of ion-exchanged water were used to obtain a monomer aqueous solution having a monomer concentration of 35% and a neutralization rate of 75%. Was dissolved and nitrogen gas was blown to drive out dissolved oxygen.
In a four-necked separable flask equipped with a stirrer, reflux condenser, thermometer, nitrogen gas inlet tube and dropping funnel, 800 parts of cyclohexane is added, and 4 parts of sucrose fatty acid ester (HLB = 6) is added as a dispersant. It was dissolved and nitrogen gas was blown to drive out dissolved oxygen. Next, the monomer aqueous solution was added to the above separable flask with stirring and dispersed. Thereafter, the bath temperature was raised to 65 ° C. to initiate the polymerization reaction, and then held at this temperature for 2 hours to complete the polymerization. After the polymerization was completed, most of the water was removed by azeotropic dehydration, followed by filtration and drying under reduced pressure at 100 ° C. to obtain a spherical water-absorbing resin having a water content of 8%. 100 parts of the resulting water-absorbent resin was mixed with 0.1 part of ethylene glycol diglycidyl ether, 3 parts of water, and 1 part of isopropanol. The resulting mixture was heated at 120 ° C. for 30 minutes, and then the particles were mixed with methanol. The water-absorbent resin 4 was obtained by processing.
(Production Example 5) Production Method of Water Absorbent Resin 5 (Containing as a Main Component the following Surface Cross-Linked Untreated Product) A 38% by mass aqueous solution (partially neutralized acrylic acid (Na Polyethylene glycol diacrylate (n = 8) was dissolved in (salt) aqueous solution) to prepare a reaction solution. Next, the reaction solution was degassed under a nitrogen gas atmosphere. Next, the reaction solution is supplied to a jacketed double-armed kneader with two sigma blades with a lid that can be opened and closed. While stirring the reaction solution, ammonium persulfate and L-ascorbic acid are used as initiators. The resulting hydrogel polymer, which was added to initiate polymerization, was taken out.
The obtained hydrogel polymer was dried with hot air. Next, the dried product is pulverized using a pulverizer, and further passed through a sieve having an opening of 850 μm to obtain an irregularly crushed water-absorbing resin (surface-crosslinked untreated product).
The water absorbent resin 5 is a water absorbent resin containing the above water absorbent resin (surface-crosslinked untreated product) as a main component (including about 70% by mass).

The tea leaves are shown below.
About tea leaves of jasmine tea Seller: ITO EN Co., Ltd. (Location: 3-47-10 Honmachi, Shibuya-ku, Tokyo)
Name: Jasmine tea Raw material name: Green tea, flower (jasmine)
Country of origin: People's Republic of China (Fujian)
Features: Jasmine tea from Fujian, China, which is made by adding natural jasmine flower scent to roasted green tea in a kettle. Made with. The leaf components are easy to dissolve in water.
Particle size: 100 mesh (aperture 150 μm) -ON is contained in 90% by mass or more. That is, the proportion of fine particles passing through a 100 mesh (mesh 150 μm) wire mesh is 10% by mass or less.
About Hojicha tea leaves Manufacturer: Aro-en Co., Ltd. Name: Special Hojicha Raw material name: About green tea green tea powder Seller: Itoen Co., Ltd. (Location: 3-47-10 Honmachi, Shibuya-ku, Tokyo)
Name: Green tea Raw material name: Green tea, dextrin, cyclodextrin, vitamin C
Country of origin: People's Republic of China, Japan Features: 60mg tea polyphenol (containing catechins) per 0.8g serving (100cc)

The physical properties of the water-absorbent resin are measured by the following method.
(A) Absorption capacity under no pressure (absorption capacity for 30 minutes under no pressure with respect to 0.90 mass% sodium chloride aqueous solution)
Under a condition of room temperature (20 to 25 ° C.) and humidity of 50 RH%, 0.20 g of a water-absorbing resin is uniformly put in a non-woven bag (60 mm × 60 mm) and sealed, and then 0.9 mass% sodium chloride at room temperature. It was immersed in an aqueous solution. After 30 minutes, the bag was pulled up, drained at 250 cm / sec ² (250 G) for 3 minutes using a centrifuge (manufactured by Kokusan Co., Ltd., centrifuge: model H-122), and then the mass W1 (g ) Was measured. Further, the same operation was performed without using the water absorbent resin, and the mass W0 (g) at that time was measured. And from these W1 and W0, the absorption capacity (g / g) under no pressure was calculated according to the following formula.
Absorption capacity under no pressure (g / g) = (W1 (g) −W0 (g)) / mass of water absorbent resin (g)
(B) The weight-average particle diameter water-absorbing resin powder was sieved with JIS standard sieves having openings of 850 μm, 500 μm, 300 μm, 150 μm, 75 μm, and 45 μm, and the residual percentage R was plotted on logarithmic probability paper. Thereby, the weight average particle diameter (D50) was read.
In addition, according to the particle size of the water-absorbent resin powder, it is necessary to add a JIS standard sieve as appropriate and perform accurate measurement.
The classification method at the time of sieving is as follows. 10.0 g of water-absorbent resin powder is used at room temperature (20 to 25 ° C.) and humidity is 50 RH%. ) And classified for 10 minutes using a vibration classifier (IIDA SIEVE SHAKER, TYPE: ES-65 type, SER. No. 0501). The weight average particle diameter (D50) is a standard sieve (aperture) particle diameter corresponding to 50% by weight of a standard sieve with a constant opening, as described in US Pat. No. 5,051,259. For example, when 50% by weight of the whole particle is classified with a standard sieve having an opening of 300 μm, the weight average particle diameter (D50) is 300 μm.
(C) Soluble content In a plastic container with a lid with a capacity of 250 ml, weigh out 184.3 g of 0.9% by mass sodium chloride aqueous solution, add 1.0 g of water-absorbing resin to the aqueous solution, and stir for 16 hours. The soluble part in it was extracted. Filtration of this extract using one sheet of filter paper (ADVANTEC Toyo Co., Ltd., product name: (JIS P 3801, No. 2), thickness 0.26 mm, retained particle diameter 5 μm) gave 50. 0 g was measured and used as a measurement solution. First, a 0.9% by mass sodium chloride aqueous solution was first titrated to pH 10 with a 0.1N aqueous NaOH solution, and then titrated to a pH 2.7 with a 0.1N aqueous HCl solution ([bNaOH]). ml, [bHCl] ml). The titration ([NaOH] ml, [HCl] ml) was determined by performing the same titration operation on the measurement solution. For example, in the case of a water-absorbing resin composed of a known amount of acrylic acid and its sodium salt, the soluble content in the water-absorbing resin is calculated by the following formula based on the average molecular weight of the monomer and the titration amount obtained by the above operation. can do. In the case of an unknown amount, the average molecular weight of the monomer is calculated using the neutralization rate obtained by titration.
Soluble content (mass%) = 0.1 × (average molecular weight) × 184.3 × 100 × ([HCl] − [bHCl]) / 1000 / 1.0 / 50.0
Neutralization rate (mol%) = (1 − ([NaOH] − [bNaOH]) / ([HCl] − [bHCl])) × 100
(D) Solid content 1.000 g of the water-absorbent resin was put in an aluminum cup, heated in a windless oven at 180 ° C. for 3 hours, and calculated by its loss on drying. Measurement is Japanese Unexamined Patent Publication No. 2000-121291, page 13.

Follow the method described.
Table 1 shows the physical properties of the water absorbent resins 3 to 5.

Next, the fire extinguishing experiment of the cigarette using the ashtray of this invention and the gel for fire extinguishing is shown.
[Example 1]: An ashtray with a circular mesh opening of 100 mesh, meshed with a 12 mm diameter, thin, cylindrical foamed polyethylene (Tahara Chemical Industries Co., Ltd., foamed polyethylene color tube) covered with aluminum foil. 7 is attached to surround the container, and is floated in a tank containing 150 g of water (see FIG. 8). I was immersed.
(Observation result: The fire extinguishes instantly by placing two lit cigarettes, and the fire extinguishing ability is high. The smell of cigarettes after the fire extinguishes remains.)
[Comparative Example 1]: A lit cigarette is put into a water tank containing 150 g of ashtray water.
(Observation results: Fire extinguished instantly, fire extinguishing ability is high. Cigarette odor remains after fire extinguishing. Cigarette odor does not disappear even after standing for 1 week, water turns brown. Water and tobacco separation takes time. .)
[Example 2]: Into a portion that receives the butts of Example 1 of the ashtray, 3 g of used coffee beans that are commercially available are placed, and then lit cigarettes are added.
(Observation result: Fire extinguished instantaneously, fire extinguishing ability is high. Coffee odor masks to some extent, but cigarette odor remains after extinguishing. The degree of brown color of water after standing for 1 week is large.)
[Example 3]: Used tea leaves (3 g) of used jasmine tea are put in the part receiving the butts of Example 1 and put on the lit cigarette. (Hereafter, the tea leaves of jasmine tea are abbreviated as jasmine tea leaves.)
(Observation results: Fire extinguished instantaneously, fire extinguishing ability is high. Although masked to some extent, cigarette odor remains after extinguishing. Used jasmine tea leaves have little deodorizing effect. Cigarette odor disappears after standing for 1 week. The water color is brown.)
[Example 4]: In place of the 100-mesh wire mesh used in the ashtray Example 1, the mesh mesh is changed to a 400-mesh wire mesh, and jasmine tea leaves (unused 3 g) are put in the portion receiving the butts, as in Example 1. Into the lit cigarette.
(Observation results: Fire extinguished instantly, fire extinguishing ability is high. High masking effect, cigarette odor disappears after extinguishing. Unused jasmine tea leaves have great deodorizing effect. Cigarette odor disappears after standing for 1 week. (The color of the water is brown, with the scent of jasmine floating.)
[Embodiment 5]: The bottom of a circular mesh 100 mesh wire mesh with an ashtray with a 12 mm diameter thin cylindrical foamed polyethylene (Tahara Kasei Kogyo Co., Ltd., foamed polyethylene color tube) covered with aluminum foil. 7 is attached in a water tank containing 150 g of water (see FIG. 9), and the part of the wire mesh that receives the cigarette shell is immersed in water when a load is applied from above. I was able to.
(Observation result: When the lighted cigarette is lightly pressed by hand against the wire mesh, the fire is extinguished instantly and has a fire extinguishing ability.
[Example 6] :: A thin cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (made by Tahara Kasei Kogyo Co., Ltd., foamed) A fragrance gel 1 (3 g) having an average particle diameter of about 5 mm is put in a butt receiver as shown in FIG. 7 attached so as to surround the four sides with a polyethylene color tube) and floated in a water tank containing 150 g of water. As a result (see FIG. 8), the fragrance gel 1 contained in the portion receiving the cigarette wrap surrounded by the aluminum foil-coated foamed polyethylene absorbs water and swells, and seems to overflow from the butt receiving portion (model diagram of FIG. 11). reference).
(Observation results: Since the gel has a large particle size, there is sufficient water between the gel particles and fire extinguishing ability. Waste cigarettes have crevice water between the gel particles, so the gel is easy to sink between the gel particles, and the gel is aromatic. There is a high deodorizing ability.
[Example 7] :: Ashtray containing fire-extinguishing gel Continuing from the state of Example 6, when 1 g of sodium chloride was added to the water tank,
The water absorption amount of the gel decreased, the proportion of the gel in the portion receiving the shell surrounded by the aluminum foil-coated foamed polyethylene decreased, and the moisture content increased (see the model diagram in FIG. 12). The gel particles are dispersed in water (the sodium chloride concentration in the gel dispersion is 0.7% by mass with respect to water).
(Observation result: The fire extinguishes instantly just by placing a lit cigarette, the fire extinguishing ability is high. The smell of the cigarette disappears after the fire extinguishes, and the waste cigarette has enough crevice water between the gel particles. (After being left for a week, the smell of cigarettes disappeared and the fragrance persisted, but the water color is brown.)

[Example 8]: Long cylindrical foamed polyethylene with a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (made by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) A gel tube (3 g) in which water is absorbed 50 times in the water-absorbent resin 5 is contained in a shell receiver as shown in FIG. When floating in the water tank (see FIG. 8), the water-absorbent resin 5 contained in the portion receiving the cigarette wrap surrounded by the aluminum foil-coated foamed polyethylene further swelled by water absorption, and it seemed to overflow from the butt receiving portion (see FIG. 8). 11).
(Observation result: Since the particle size of the gel is small, there is little interstitial water between the gel particles, but there is a fire extinguishing ability. The gels adhere to each other to form a granulated product, and the waste tobacco is difficult to sink between the gel particles. )
[Example 9]: Continuing from the state of the ashtray Example 8 in which the fire-extinguishing gel was contained, 1 g of sodium chloride was added to the water tank.
The water absorption amount of the gel decreased, the proportion of the gel in the portion receiving the shell surrounded by the aluminum foil-coated foamed polyethylene decreased, and the moisture content increased (see FIG. 12). The gel particles are dispersed in water (the sodium chloride concentration in the gel dispersion is 0.7% by mass with respect to water).
(Observation result: After the addition of sodium chloride, crevice water was generated between the gel particles, and the fire extinguishing ability was higher than before addition. Waste cigarettes easily sink in the gel layer because there is crevice water between the gel particles.)
[Example 10]: A thin cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil at the bottom of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (made by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) A water tank containing 150 g of water on which a gel (3 g) in which water is absorbed 50 times in a water absorbent resin 5 is placed on a wire mesh of a butt receiver as shown in FIG. As shown in FIG. 9, the portion of the wire mesh that receives the cigarette shell on which the gel is placed absorbs water from the top (increases to 14 g) once the load is applied from the top, and becomes sufficiently wet.
(Observation result: When the lighted cigarette is lightly pressed by hand, the fire is extinguished instantaneously, and there is a fire extinguishing ability. Gels adhere to each other to form a granulated product, and waste tobacco is difficult to sink between the gel particles. .)
[Example 11]: A thin cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil on an upper part of a 100-mesh wire mesh having an ashtray circular shape containing a fire extinguishing gel (made by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) A water tank containing 150 g of water in which a gel (3 g) in which water is absorbed 50 times in the water-absorbent resin 3 is contained in a butt shell as shown in FIG. As shown in FIG. 8, the water-absorbent resin 3 contained in the portion receiving the butt surrounded by the aluminum foil-coated foamed polyethylene further absorbs water and swells and seems to overflow from the butt-receiving portion (FIG. 11). reference).
(Observation result: There is little interstitial water between the gel particles, but there is a fire extinguishing ability. Gels easily adhere to each other, and waste tobacco is difficult to sink between the gel particles.)
[Example 12]: Continuing from the state of the ashtray Example 11 in which a fire extinguishing gel was incorporated, 1 g of sodium chloride was added to the water tank.
The water absorption of the gel is very low, the part that receives the cigarette shell surrounded by the aluminum foil-coated foamed polyethylene becomes fully immersed in water, the gel is dispersed at the bottom, and the fire extinguishing ability is greatly improved than before adding sodium chloride (See FIG. 12). The decrease in water absorption was remarkably seen compared to other water absorbent resins. Since waste tobacco has sufficient water between the gel particles, it tends to sink between the gel particles. (The sodium chloride concentration in the gel dispersion is 0.7% by mass with respect to water).
(Observation results: After addition of sodium chloride, crevice water was generated between the gel particles, and the fire extinguishing ability was greatly improved as compared to before the addition. Waste cigarettes easily sink between the gel particles because there is sufficient crevice water between the gel particles. .)
[Example 13]: Ashtray containing fire-extinguishing gel Continuing from the state of Example 12, when 150 g of water was added to lower the salt concentration, the water absorption of the gel was slightly improved, but it was still insufficient. It is fully immersed in water.
The degree of swelling of the water absorbent resin can be adjusted by changing the salt concentration.
(The sodium chloride concentration in the gel dispersion is 0.3% by mass with respect to water)
[Example 14]: A thin cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (manufactured by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) A water tank containing 150 g of water in which a gel (3 g) in which water is absorbed 50 times in water-absorbent resin 4 is contained in a butt shell as shown in FIG. As shown in FIG. 8, the water-absorbent resin 4 contained in the portion receiving the butt surrounded by the aluminum foil-coated foamed polyethylene further absorbs water and swells and seems to overflow from the butt-receiving portion (FIG. 11). reference).
(Observation result: fire extinguishing ability. Since there is little crevice water between gel particles, waste tobacco is hard to sink in the gel layer.)
[Example 15]: Continuing from the state of the ashtray Example 14 in which the gel for extinguishing fire was added, 1 g of sodium chloride was added to the water tank.
The water absorption of the gel is very low, the part that receives the cigarette shell surrounded by the aluminum foil-coated foamed polyethylene becomes fully immersed in water, the gel is dispersed at the bottom, and the fire extinguishing ability is greatly improved than before adding sodium chloride (See FIG. 12).
(Observation result: The fire extinguished instantly just by placing a lit cigarette. The smell of the cigarette after the fire extinguishes remains, and the waste tobacco has enough crevice water between the gel particles, so it easily sinks between the gel particles. (The sodium chloride concentration in the gel dispersion is 0.7% by mass with respect to water)
If there is a water-absorbing resin water-absorbing gel, the turbidity of water is reduced, and the degree of turbidity of water after standing for 1 week is small. This is thought to be due to the slow elution rate of tobacco components into water. )

[Example 16]: Long cylindrical foamed polyethylene with a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 60 mesh wire net containing a fire extinguishing gel (made by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) A water tank containing 150 g of water in which a gel (3 g) in which water is absorbed 50 times in water-absorbent resin 4 is contained in a butt shell as shown in FIG. As shown in FIG. 8, the water-absorbent resin 4 contained in the portion receiving the butt surrounded by the aluminum foil-coated foamed polyethylene further absorbs water and swells and seems to overflow from the butt-receiving portion (FIG. 11). reference).
(Observation result: Fire extinguishing ability. Because there is little interstitial water between gel particles, waste tobacco is difficult to sink between gel particles.)
[Example 17]: Ashtray containing fire-extinguishing gel Continuing from the state of Example 16, when 1 g of sodium chloride was added to the water tank,
The water absorption of the gel is very low, the part that receives the cigarette shell surrounded by the aluminum foil-coated foamed polyethylene becomes fully immersed in water, the gel is dispersed at the bottom, and the fire extinguishing ability is greatly improved than before adding sodium chloride (See FIG. 12). Furthermore, jasmine tea leaves (unused 1 g) were put on the gel (tea leaves in the gel dispersion were 0.7% by mass with respect to water).
(Observation result: The fire extinguished instantly just by placing a lit cigarette. The smell of the cigarette after fire extinguishes is relatively low, and the waste tobacco has enough water, so it easily sinks in the gel layer. Gel dispersion The concentration of sodium chloride in the water is 0.7% by mass with respect to the water.The water after leaving for one week is turbid due to the dissolution of the components of the jasmine tea leaves, and the cigarette odor remains low. (The water-absorbing gel is shrinking further.)
[Example 18]: A thin cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (manufactured by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) In the butt receiver as shown in Fig. 7 attached so as to surround the four sides with a colored tube made of), jasmine tea leaf (unused 1g) and gel (3g) in which water absorption resin 3 has absorbed water 50 times are contained. (The tea leaves in the gel dispersion are 0.7% by mass with respect to water), floated in a water tank containing 150 g of water (see FIG. 8), and the part that receives the butts surrounded by the aluminum foil-coated polyethylene foam At first, the water-absorbing resin 3 contained in the water was further swollen by absorbing water, and it seemed to overflow from the shell-receiving portion (see FIG. 11). However, the amount of water absorption decreased as the components of jasmine tea leaf eluted, and after 6 hours, there was moderate crevice water between the gels and the gel surface was sufficiently wet.
(Observation result: Fire extinguishing ability. There is interstitial water between gel particles, and waste tobacco sinks between gel particles. After one week of the fire extinguishing experiment, the water becomes cloudy brown, but the cigarette smell is low.)
[Example 19]: Long cylindrical foamed polyethylene having a diameter of 12 mm covered with aluminum foil on the top of an ashtray circular mesh 100 mesh wire net containing a fire extinguishing gel (manufactured by Tahara Kasei Kogyo Co., Ltd., foamed polyethylene) In a butt receiver as shown in FIG. 7 attached so as to surround the four sides with a colored tube), jasmine tea leaves (unused 5 g) and gel (3 g) in which water is absorbed 50 times in the water absorbent resin 3 are contained. (The tea leaves in the gel dispersion are 3.3% by mass with respect to water), floating in a water tank containing 150 g of water (see FIG. 8), the part receiving the cigarette butt surrounded by the aluminum foil coated polyethylene foam At first, the water-absorbing resin 3 contained in the water was further swollen by absorbing water, and it seemed to overflow from the shell-receiving portion (see FIG. 11). However, the amount of water absorption decreased as the tea components eluted, and after 6 hours, there was moderate crevice water between the gels and the gel surface was sufficiently wet.
(Observation result: Fire extinguishing ability. There is interstitial water between the gel particles, and the waste tobacco sinks between the gel particles. After one week of the fire extinguishing experiment, the water turns brown, but the cigarette smell is low. The water absorption ratio of the water-absorbing gel decreases and the crevice water is moderately retained between the gel particles. The degree of water absorption is greatly reduced, and the degree of swelling of the water-absorbent resin can be adjusted according to the amount of tea leaves added and the passage of time.
[Comparative Example 2]: Fire extinguishing gel (dispersion)
The water-absorbent resin 5 used in Examples 8 to 10 has a particle size distribution shown in Table 1, and the ratio of fine particles having a particle size of less than 150 μm is as high as about 60% by mass.
Moreover, the weight average particle diameter is as small as 100 μm. When the proportion of the fine particles is high, even when an inorganic salt (0.7% by mass) is added, it becomes insufficient to secure water between the gel particles at the time of water absorption, and the fluidity of the gel dispersion becomes low. For this reason, gels adhere to each other and granulate easily, and waste tobacco does not easily sink between the gel particles. Because it absorbs water, it has fire extinguishing ability.
[Example 20]: Fire extinguishing gel (dispersion)
The water-absorbent resin 3 used in Examples 11 to 13 has a particle size distribution shown in Table 1, and the ratio of fine particles having a particle size of less than 150 μm is as low as about 11% by mass. Further, the weight average particle size is as large as 201 μm. When an inorganic salt is added (0.7% by mass, 0.3% by mass), the proportion of fine particles is low, the weight average particle size is large, and the particles are spherical particles. The fire extinguishing ability is high. Due to the high fluidity of the gel dispersion, the waste tobacco tends to sink between the gel particles.
[Example 21]: Fire extinguishing gel (dispersion)
The water-absorbent resin 4 used in Examples 14 to 16 has a particle size distribution shown in Table 1, and the proportion of fine particles having a particle size of less than 150 μm is as low as about 16% by mass. Further, the weight average particle diameter is as large as 185 μm. Addition of inorganic salt (0.7% by mass, the proportion of fine particles is low, the weight average particle size is large, and the particles are spherical. Because the fluidity of the gel dispersion is high, waste tobacco tends to sink between the gel particles.
[Example 22]: Fire extinguishing gel (dispersion)
The fire-absorbing gel containing water-absorbent resin 4, jasmine tea leaf, inorganic salt and water used in Example 17 was obtained by further adding 0.7% by mass of jasmine tea leaf to water in addition to the fire-extinguishing gel of Example 21. Thus, in addition to the fire extinguishing ability, it becomes a fire extinguishing gel having the ability to deodorize cigarettes. Jasmine tea leaves contain unused green tea, and the proportion of fine particles that pass through a 100 mesh wire net is as low as 10% by mass or less, so the tea leaf extract components gradually elute into the water. As the water content decreases, the amount of crevice water increases, resulting in a gel dispersion with higher fluidity.
[Example 23]: Fire extinguishing gel (dispersion)
The fire-absorbing gel containing water-absorbent resin 3, jasmine tea leaves and water used in Example 18 was obtained by adding 0.7% by mass of unused jasmine tea leaves to water. It becomes a fire-fighting gel with deodorant ability.
When the components of jasmine tea leaves are eluted in water, the water absorption capacity of the water-absorbent resin is lowered, so that crevice water is generated between the gel particles and the fluidity is obtained.
[Example 24]: Fire extinguishing gel (dispersion)
The fire-absorbing gel containing water-absorbent resin 3, jasmine tea leaves and water used in Example 19 was obtained by adding 3.3% by mass of unused jasmine tea leaves to water. It becomes a fire-fighting gel with deodorant ability.
When the components of jasmine tea leaves are eluted in water, the water absorption capacity of the water-absorbent resin is lowered, so that crevice water is generated between the gel particles and the fluidity is obtained.

Next, the deodorization result after extinction of the tobacco using various materials is shown.
The following materials were added into the aluminum cup.
[Example 25]: Fire extinguishing gel (dispersion)
Fragrance gel 2 (approx. 0.6g) + water total (20g)
The smell of a single lit cigarette after fire; the cigarette odor disappears.
Odor after standing for 1 week; tobacco odor remains extinguished.
[Comparative Example 3]: Water only (20 g)
A single lit cigarette smell after extinguishing; the cigarette odor remains.
Odor after standing for 1 week; cigarette odor remains. The color of the water is also dirty. A lot of ashes sink to the bottom.
[Example 26]: Jasmine tea leaves (unused 1 g) + total with water (15 g)
The smell of a single lit cigarette after fire; the cigarette odor disappears.
Odor after standing for 1 week; tobacco odor remains extinguished.
[Example 27]: Hojicha tea leaves (Aro-en; unused 1 g) + water total (15 g)
A single lit cigarette smell after extinguishing; the cigarette odor remains.
Odor after one week; cigarette odor remained, but to some extent it was deodorized.
Next, comparative experiments (Examples 28 and 29) in which the water absorption capacity of the water-absorbent resin decreases with the tea leaf extract component are shown.
[Example 28]: Gel (3 g) in which water is absorbed 50 times in water-absorbent resin 4 + jasmine tea leaf (1 g) + water 27 g...
The above composition is a fire extinguishing gel containing 0.2% by mass of a water-absorbing resin, 3.2% by mass of tea leaves, and 96.6% by mass of water.
[Example 29]: Gel (3 g) in which water is absorbed 50 times in water-absorbent resin 4 + 27 g of water.
The above formulation is a fire-extinguishing gel having a water-absorbing resin content of 0.2% by mass and water of 99.8% by mass.
From the above experiment, the following was observed.
Fire extinguishing materials containing fragrances and tea leaves can reduce tobacco odor.
The water absorption capacity of the water-absorbent resin as a component of the tea leaf extract decreases with time. It is also an alternative to adding inorganic or organic salts.

[Example 30]: Water-absorbent resin 4 (5 g) and green tea powder (1 g) were dry-mixed. 1 g of the mixture was put into a water tank, and 40 g of water was added. Green tea melted quickly because it was powdery.
(Water absorbent resin 2.0 mass%, green tea powder 0.4 mass%, water 97.6 mass%)
Since there was little gap water between the gels, 61 g of green tea (green tea powder 1 g + water 60 g) was further added. (0.8% by mass of water absorbent resin, 1.2% by mass of green tea powder, 98.0% by mass of water)
In order to further increase the gap water between the gels, 3 g of green tea powder was added.
(Water absorbent resin 0.8% by mass, green tea powder 4.0% by mass, water 95.2% by mass)
After this addition, when the mixture was stirred with a spoon, the release of water from the gel was remarkably observed (high fire extinguishing ability). Next, 2 g of sodium chloride was added to shrink the gel (0.8% by mass of water absorbent resin, 3.9% by mass of green tea powder, 93.4% by mass of water, 1.9% by mass of sodium chloride). By this addition, the release of water from the gel was very large, and the gel hardly absorbed water and became liquid (reduction of the trouble of collecting the swollen gel after extinguishing the fire).
[Example 31]: 3 g of natural pumice (release source: Kikuron Co., Ltd.) about 2 cm square (thickness 1 cm) is floated on the natural pumice in a water tank to which 200 g of water and 2 g of sodium chloride are added A small amount of water-absorbing resin 4 was placed with a mesh 400 mesh mesh (see FIG. 13). The water-absorbent resin absorbed water and had water between the gels and was sufficiently wet, so that the fire extinguishing ability was high. When only natural pumice was floated, it was observed that the upper surface was wetted by water. Since the water-absorbing resin absorbs the water on the upper surface, drilling a hole near the center of this natural pumice from above will further improve the wet condition of the upper surface of the natural pumice, and between the water-containing resin hydrogels More crevice water. (If a hole is made in natural pumice, water will permeate directly from the hole and the fire extinguishing capacity of the hydrogel will increase.)
[Example 32]: A HIPE foam of about 2 × 5 cm square (water absorption capacity of ion-exchanged water: 37 g / g) is floated in a water tank to which 200 g of water and 2 g of sodium chloride are added. On the HIPE foam, A small amount of water-absorbing resin 4 was placed (see FIG. 14). Since the water-absorbent resin absorbed water, and there was water between the gels and was sufficiently wet, the fire extinguishing ability was high. When only the HIPE foam was floated, it was observed that the upper surface was wetted with water. The water-absorbing resin absorbs water on the upper surface, thereby enhancing the fire extinguishing ability of the water-containing gel.

It is a perspective view of the stand type ashtray which concerns on 1st embodiment of this invention. It is a disassembled perspective view of the stand type ashtray which concerns on 1st embodiment of this invention. It is sectional drawing of the ashtray main body of FIG. It is sectional drawing of other embodiment of an ashtray main body. It is sectional drawing of other embodiment of an ashtray main body. It is sectional drawing of other embodiment of an ashtray main body. It is the figure seen from right above the buttocks receptacle. It is a side view when a cigarette butt is floated on the water tank. It is a side view when a cigarette butt is floated on the water tank. It is sectional drawing of the ashtray main body which concerns on 2nd embodiment of this invention. It is a mode when the particulate water-absorbent resin is contained in the cigarette housing accommodating space of FIG. It is a mode when sodium chloride is added to the water tank in the state of FIG. It is a side view in which water-absorbent resin is hold | maintained on a natural pumice and is floating in the water tank. It is a side view in which the water-absorbent resin is held on the HIPE foam and is floating in the water tank.

Explanation of symbols

(1) ... Water tank (2) ... Refractory material with a lower specific gravity than water (3) ... Reticulated container (4) that houses the butts ... Water-absorbing material (water-absorbing resin)
(5) ... Water (6) ... Upper lid (7) ... Butt opening (8) ... Receiving base (9) ... Stainless steel wire mesh (10) ... Butt housing accommodation space (11) ... Water absorbent resin (12) ... Natural pumice (13) ... HIPE form

Claims (14)

A fire-extinguishing gel comprising a water-absorbing resin, a plant component, and water. Furthermore, inorganic gel or organic salt is included, The gel for fire extinguishing of Claim 1 characterized by the above-mentioned. The fire-absorbing gel according to claim 1 or 2, wherein the water-absorbent resin and the plant component are in the form of particles. The fire extinguishing gel according to any one of claims 1 to 3, wherein the plant component is tea leaf and / or tea leaf extract. The fire extinguishing gel according to any one of claims 1 to 4, wherein a ratio of fine particles having a particle diameter of less than 150 µm in the water absorbent resin before water absorption is 20 mass% or less. A fire extinguishing gel containing a water absorbent resin, an inorganic salt or an organic salt, and water, wherein the proportion of fine particles having a particle diameter of less than 150 μm in the water absorbent resin before water absorption is 20% by mass or less. Fire-fighting gel. The fire-absorbing gel according to any one of claims 1 to 6, wherein the water-absorbent resin is a polyacrylic acid (salt) -based crosslinked polymer. The fire-absorbing gel according to any one of claims 1 to 7, wherein the water-absorbent resin floats on a water surface. A fire extinguishing method using the fire extinguishing gel according to claim 1. The fire extinguishing method according to claim 9, wherein the fire extinguishing method is used for extinguishing cigarettes in an ashtray. A fire extinguishing method using a water-containing resin hydrogel floating on the water surface. An ashtray characterized by containing a water-containing resin hydrogel floating on the water surface. A water tank (1) for storing water, a refractory material (2) having a specific gravity smaller than that of water, and a net-like container (3) for containing a cigarette butt,
The ashtray characterized in that the net-like container (3) floats on the water surface of the water tank (1) in a state of being joined to the refractory material (2). The ashtray according to claim 13, wherein the net-like container (3) floats on the water surface due to the presence of the fire-extinguishing gel according to claims 1-8.

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