JPH0451188B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fire extinguishing agent that effectively prevents water damage and has greatly increased extinguishing power, particularly a fire extinguishing agent that is effective against wood fires.

[Conventional technology]

In recent building fires such as apartment buildings,
Not only does the fire itself cause damage to the floor where the fire occurred and its surroundings, but also water damage to the floor below the floor where the fire occurred due to the large amount of water being sprayed occurs, and this has become a major social problem.

Traditionally, fire departments have tried to deal with water damage by adjusting water nozzles to reduce the amount of water being sprayed, covering accumulated water with tarpaulins, or using residual water treatment equipment. It was processed after the fact. In addition, fire extinguisher and extinguishing agent manufacturers are searching for extinguishing agents that can achieve excellent extinguishing effects with a small amount of water. Fire extinguishing agent (Unexamined Japanese Patent Publication No. 1983-
No. 192573) has also been reported.

On the other hand, recently, research has been conducted on methods of gelling water by spraying so-called super-absorbent resins, which are used in soil water retention agents and absorption enhancers for sanitary materials, at the same time as water is released when extinguishing a fire. A fire extinguishing method using water containing this super absorbent resin
No. 076966), a fire extinguishing agent made by adding a super absorbent resin to water, a combination of carboxymethyl cellulose and other water-soluble polymer compounds to impart tackiness, and sulfates and other heat-resistant inorganic organic compounds. A fire extinguishing agent (Japanese Patent Application Laid-open No. 56-049167) has also been proposed that is used in combination with fire extinguishers to provide anti-reignition properties.

[Problem that the invention seeks to solve]

However, restrictions on the amount of water sprayed when extinguishing a fire cannot be adopted lightly, as there is a risk of unduly expanding fire damage. In addition, conventional extinguishing agents containing potassium carbonate as the main ingredient, which is said to have a fire extinguishing effect even with a small amount of water, are used only in small amounts that do not cause water damage, even if it is possible to reduce the amount of water sprayed slightly. The fire extinguishing power is not strong enough to suffice with the amount of water sprayed.

In addition, with conventional technology that uses superabsorbent resin for extinguishing fires, a large amount of water is absorbed into the superabsorbent resin and used to extinguish the fire, so it provides excellent cooling effects and air blockage over a relatively long period of time. It is thought that it also has the effect of preventing water damage. However, in reality, it has been extremely difficult to simultaneously obtain both excellent fire extinguishing power and water damage prevention performance in the event of a fire. In other words, although water gelled by superabsorbent resin does have a cooling effect, an air blocking effect, and an excellent water damage prevention effect, it lacks a flame-retardant effect on objects that are subject to fire, making it easy to re-ignite. There was a problem.

In addition, when sulfates and other heat-resistant inorganic organic compounds are used in combination to prevent such flare-ups, while a certain degree of flare-preventing effect can be obtained, the water absorption capacity of the super absorbent resin is extremely reduced. The water absorption stability is destroyed, and the drug mixture in a good gelatinous state is separated into water and super absorbent resin, resulting in a sustained cooling effect and air blocking effect, which are the characteristics of super absorbent resin, as well as a water damage prevention effect. There was a serious problem of damage to the This phenomenon occurs because the so-called superabsorbent resin is made of an electrolyte polymer that has been insolubilized by low-density crosslinking and has ionic groups, and according to the FLORY equation, the addition of water-soluble salts as described above This is thought to be mainly due to an increase in the ionic strength of the external solution.

The present invention aims to solve the above-mentioned drawbacks of the prior art and to provide a fire extinguishing agent that simultaneously exhibits both flame-retardant extinguishing power and water damage prevention effect in the event of a fire.

[Means for solving problems and their effects]

The present inventors have discovered that when a superabsorbent resin is added to water to prepare a fire extinguishing agent, it is possible to impart fire extinguishing power with excellent flame retardant properties without impairing its good gelling state, that is, water absorption stability. As a result of repeated research on the possibility of a combination ingredient, it was discovered that red phosphorus was suitable as the combination ingredient, and the present invention was completed.

That is, the fire extinguishing agent according to the present invention is made by adding a super absorbent resin and phosphorus excluding yellow phosphorus to water.

In the present invention, the superabsorbent resin is made of an electrolyte polymer that is insolubilized by low-density crosslinking and has ionic groups, as described above,
Examples of such superabsorbent resins are saponified starch-acrylonitrile graft copolymers, starch-acrylate graft copolymers, cross-linked polyacrylates, vinyl alcohol-acrylate block copolymers, cross-linked polyvinyl alcohol, cross-linked carboxymethyl cellulose salt, etc.

It is preferable to select a super absorbent resin with a water absorption coefficient (weight after water absorption/weight before water absorption) of 500 or more. If it is less than 500, the chemical mixture in a gel state will adhere to the fire target. However, the water may separate and leak easily. In addition, it is preferable that the super absorbent resin is added in an amount of 0.1 to 2 parts by weight, particularly 0.3 to 1 part by weight, per 100 parts by weight of water.If the amount added is less than 0.1 part by weight, the chemical mixture becomes a fire hazard. Even if it adheres to objects, water tends to separate and leak, and if the amount added exceeds 2 parts by weight, the chemical mixture loses fluidity, making release work and other handling during fire extinguishing difficult.

In addition, in the present invention, phosphorus other than yellow phosphorus is
Refers to single substances or mixtures of red phosphorus, purple phosphorus, black phosphorus, etc., and also includes those that have been modified or modified, mixed with other substances, and coated with other substances. do. It is preferable that 0.1 to 1 part by weight of phosphorus, excluding yellow phosphorus, be added to 100 parts by weight of water, and when the amount added is less than 0.1 part by weight, the flame retardant effect of phosphorus is not sufficient. If the amount of phosphorus added exceeds 1 part by weight, there will be almost no effect of improving flame resistance corresponding to the excessive addition, and since phosphorus is relatively expensive, the extinguishing cost per unit area of extinguishing area will decrease. This is undesirable because it increases the amount of phosphorus and increases the possibility that phosphorus will ignite.

Incidentally, powder fire extinguishing agents have already been reported in which phosphorus other than yellow phosphorus, such as red phosphorus, is added to the powder fire extinguishing agents to enhance their ability to extinguish wood fires in particular (Japanese Patent Laid-Open No. 56-043967). , in the present invention,
By mixing phosphorus (excluding yellow phosphorus) into the gelatinized state of super-absorbent resin, which is completely different from powder extinguishing agents, the water absorption of super-absorbent resin is added to the gel that has sufficiently absorbed water. The gel fully exhibits its cooling effect, air blocking effect, and water damage prevention effect without reducing the force and separating water. , and continuously acts on the surface of the object under fire, effectively imparting flame retardance.

In the present invention, by adding urea to water in addition to the superabsorbent resin and phosphorus other than yellow phosphorus, expensive phosphorus can be used without reducing the water absorption power of the superabsorbent resin. The amount can be reduced. Here, urea includes urea, isobutyraldehyde-processed urea, acetaldehyde-processed urea, guanylurea, formaldehyde urea, oxamide, and the like. Such urea, in relation to the amount of phosphorus added, is 0.1 parts by weight per 100 parts by weight of water.
It is preferable to add up to 1 part by weight.

If necessary, other flame retardant components, fire extinguishing components, adhesive components, stabilizing components, etc. may be added to the fire extinguishing agent according to the present invention, as long as they do not reduce the water absorption capacity of the super absorbent resin. good.

Example 1 Sumikagel N-100 (sodium polyacrylate-based super absorbent resin manufactured by Sumitomo Chemical Co., Ltd., water absorption capacity approximately 1000) was added to 100 parts of water (parts by weight, the same applies hereinafter).
A sample mixture was prepared by mixing 0.3 parts of red phosphorus and 0.1 parts of red phosphorus.

When the mixture was placed on a 20-mesh mesh, no water was observed to fall through the mesh, indicating excellent water absorption stability.

In addition, when we immersed about half of the above mixed solution into a piece of paper with a width of 3 cm and a length of 20 cm, dried it at 60°C for 1 hour, and then ignited it from the edge of the non-soaked part, about half of the dipped part did not burn. , showing relatively good flame retardancy.

Example 2 A sample mixture was prepared by mixing 0.3 parts of Sumikagel N-100 and 0.3 parts of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a net-laying test in the same manner as in Example 1, it showed the same excellent water absorption stability as in Example 1.

Further, when the above-mentioned mixed solution was subjected to the immersion paper burning test in the same manner as in Example 1, the immersed portion remained almost unburned, showing superior flame retardancy than in Example 1.

Example 3 A sample liquid mixture was prepared by mixing 0.3 parts of Sumikagel N-100 and 0.5 parts of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, it showed excellent water absorption stability and excellent flame retardant properties similar to those in Example 2.

Also, fill a fire extinguisher with the above mixed liquid 3,
When subjected to an extinguishing test for an A-1 unit fire based on the "Ministerial Ordinance Establishing Technical Standards for Fire Extinguishers," there was no "ignition" or "flame" even after 2 minutes had elapsed after the complete emission, and the fire was completely extinguished. It was hot.

On the other hand, for comparison, when a fire extinguisher was filled with water only 3 and subjected to an extinguishing test for an A-1 unit fire, the fire re-ignited in just 12 seconds after the entire amount had been emitted. In addition, a fire extinguisher was filled with a mixed solution (corresponding to Comparative Example 1 described below) 3 made by mixing 0.3 parts of Sumikagel N-100 with 100 parts of water, and subjected to an extinguishing test for an A-1 unit fire. , after full radiation
It ignited again in 31 seconds.

Example 4 0.5 part of Sunwet IN-1000 (starch-acrylic acid graft polymer superabsorbent resin manufactured by Sanyo Chemical Industries, Ltd., water absorption capacity approximately 1000) was added to 100 parts of water.
A sample mixture was prepared by mixing 0.1 part of red phosphorus.

When the mixed solution was subjected to a net-laying test and a soaked paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and relatively good flame resistance as in Example 1.

Example 5 A sample liquid mixture was prepared by mixing 0.5 parts of Sunwet IM-1000 and 0.3 parts of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, it showed excellent water absorption stability and excellent flame retardant properties similar to those in Example 2.

Example 6 A sample liquid mixture was prepared by mixing 0.5 parts of Sunwet IM-1000 and 0.5 parts of red phosphorus in 100 parts of water.

When the mixed solution was subjected to the mesh test and soaked paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and flame retardancy as in Example 2.

Example 7 100 parts of water were mixed with 1.0 part of Aqua Keep 10SH (polyacrylate-based super water-absorbent resin manufactured by Seitetsu Kagaku Kogyo Co., Ltd., water absorption capacity of about 1000) and 0.1 part of red phosphorus,
A sample mixture was prepared.

When the mixed solution was subjected to a net-laying test and a soaked paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and relatively good flame resistance as in Example 1.

Example 8 A sample mixture was prepared by mixing 1.0 part of Aqua Keep 10SH and 0.3 part of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a net-laying test and a soaked paper burning test in the same manner as in Example 1, it exhibited excellent water absorption stability and excellent flame retardancy similar to those in Example 2.

Example 9 Add 0.3 parts of Sumikagel N-100 and urea to 100 parts of water.
A sample mixture was prepared by mixing 0.1 part of red phosphorus and 0.1 part of red phosphorus.

When the mixed solution was subjected to a net-laying test and a soaked paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and relatively good flame resistance as in Example 1.

Example 10 Add 0.3 parts of Sumikagel N-100 and urea to 100 parts of water.
A sample mixture was prepared by mixing 0.3 parts of red phosphorus and 0.1 parts of red phosphorus.

When the mixed solution was subjected to a net-laying test and a soaked paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and relatively good flame resistance as in Example 1.

Example 11 Add 0.3 parts of Sumikagel N-100 and urea to 100 parts of water.
A sample mixture was prepared by mixing 0.5 part of red phosphorus and 0.1 part of red phosphorus.

When the mixed solution was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, it showed excellent water absorption stability and excellent flame retardant properties similar to those in Example 2.

Example 12 A sample liquid mixture was prepared by mixing 0.5 part of Sumikagel N-100, 0.1 part of isobutyraldehyde-processed urea, and 0.3 part of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a mesh test and a immersion paper burning test in the same manner as in Example 1, it showed the same excellent water absorption stability and flame retardancy as in Example 2.

Example 13 A sample liquid mixture was prepared by mixing 0.5 parts of Sumikagel N-100, 0.3 parts of formaldehyde-processed urea, and 0.3 parts of red phosphorus in 100 parts of water.

When the mixed solution was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, it showed excellent water absorption stability and excellent flame retardant properties similar to those in Example 2.

Also, fill a fire extinguisher with the above mixed liquid 3,
When subjected to an extinguishing test for an A-1 unit fire, there was no "burning" or "flame" even after 2 minutes had elapsed after the complete emission, and the fire was completely extinguished.

Next, let's look at the floor height to make it look like an actual apartment.
A hut with a ceiling measuring 66m long x 6m wide x 2.4m high was built on a 1.5m floor using concrete blocks, with openings of 2m x 1.5m in the surrounding walls at four locations, and holes with a diameter of 10mm in the floor.
mm round holes were made at intervals of 50 cm, a device was installed under the floor to measure the amount of water that leaked through the holes, and 500 kg of lumber was loaded into the shed, ignited, and burned for 5 minutes, causing a fire. A model was prepared.
Next, using a mixing device, Sumikagel N-100, formaldehyde-processed urea, and red phosphorus were mixed and added to the fire model in an amount designed to have the composition of this example. /
When we conducted a fire extinguishing test by spraying water from a water nozzle with a water discharge capacity of 1 minute, the fire was completely extinguished in 1 minute and 54 seconds.
Moreover, not a single drop of water leaked from the 10mm hole in the floor.

On the other hand, for comparison, when we conducted a fire extinguishing test on the above fire model by spraying only water from a similar water spray nozzle, it took 4 minutes and 38 seconds to extinguish the fire.
Additionally, 270 water leaked from a hole in the floor. Also,
For the above fire model, use a mixing device to
While mixing and adding Sumikagel N-100 in an amount designed to have a composition of 0.5 parts of Sumikagel N-100 to 100 parts (corresponding to Comparative Example 2 described later), water was sprayed from the same water spray nozzle. When a fire extinguishing test was conducted, no water leaked from the holes in the floor, but it took 3 minutes and 54 seconds to extinguish the fire.

Example 14 Add 0.5 parts of Sumikagel N-100 and urea to 100 parts of water.
A sample mixture was prepared by mixing 0.5 parts of red phosphorus and 0.3 parts of red phosphorus.

When the mixed solution was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, it showed excellent water absorption stability and excellent flame retardant properties similar to those in Example 2.

Comparative Examples 1-2 In Comparative Example 1, Sumikagel N-100 was added to 100 parts of water.
Sample mixtures were prepared by mixing 0.3 parts of Sumikagel N-100 in Comparative Example 2 and 0.5 parts of Sumikagel N-100.

When each of these mixed liquids was subjected to a mesh test in the same manner as in Example 1, all of them showed the same excellent water absorption stability as in Example 1.

However, when each of the above mixed liquids was subjected to the immersion paper burning test in the same manner as in Example 1, all of them burned out without leaving any immersed portions, showing non-flame retardant properties.

Comparative Examples 3 to 5 In Comparative Example 3, Sumikagel N-100 was added to 100 parts of water.
In Comparative Example 4, 0.5 part of Sumikagel N-100 and 0.5 part of ammonium phosphate were mixed, and in Comparative Example 5, 1.0 part of Sumikagel N-100 and ammonium phosphate were mixed.
A sample mixture solution was prepared by mixing 0.5 parts of each.

When each of these mixed solutions was subjected to the immersion paper combustion test in the same manner as in Example 1, all of them showed relatively good flame retardancy as in Example 1.

However, when each of the above mixed liquids was subjected to a mesh loading test in the same manner as in Example 1, water fell through the mesh, indicating water absorption instability.

Comparative Examples 6 to 8 Sumikagel N-100 was added to 100 parts of water in Comparative Example 6.
In Comparative Example 7, 0.5 part of Sumikagel N-100 and 0.5 part of guanidine phosphate were mixed, and in Comparative Example 8, 1.0 part of Sumikagel N-100 and guanidine phosphate were mixed. A sample mixture solution was prepared by mixing 0.5 parts of each.

When each of these mixed liquids was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, both showed relatively good flame retardancy as in Comparative Examples 3 to 5, but there was concern about water absorption. It showed qualitative results.

Comparative Examples 9 to 11 In Comparative Example 9, Sumikagel N-100 was added to 100 parts of water.
Comparative Example 10 by mixing 0.3 parts and 0.3 parts of melamine phosphate.
In Comparative Example 11, 0.5 part of Sumikagel N-100 and 0.5 part of melamine phosphate were mixed.
Mix 1.0 part of -100 and 0.5 part of melamine phosphate,
Sample mixtures were prepared for each.

When each of these mixed liquids was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, both showed relatively good flame retardancy as in Comparative Examples 3 to 5, but there was concern about water absorption. It showed qualitative results.

Comparative Examples 12-14 In Comparative Example 12, Sumikagel N-100 was added to 100 parts of water.
In Comparative Example 13, 0.5 part of Sumikagel N-100 and 0.5 part of urea phosphate were mixed, and in Comparative Example 14, Sumikagel N-100 was mixed.
Sample mixtures were prepared by mixing 1.0 part of urea phosphate and 0.5 part of urea phosphate.

When each of these mixed liquids was subjected to a mesh test and a soaked paper burning test in the same manner as in Example 1, both showed relatively good flame retardancy as in Comparative Examples 3 to 5, but there was concern about water absorption. It showed qualitative results.

Comparative Example 15 Add 0.3 parts of Sumikagel N-100 and urea to 100 parts of water.
0.5 parts were mixed to prepare a sample mixture.

When the mixed liquid was subjected to the net loading test and the soaked paper burning test in the same manner as in Example 1, Comparative Examples 1 to 2
Similarly, it exhibited excellent water absorption stability and was non-flame retardant.

Comparative Example 16 Each of the above Comparative Examples 1 to 15 was subjected to the net placement test and soaked paper burning test in the same manner as in Example 1, using Sunwet IM-1000 and Aqua Keep 10SH instead of Sumikagel N-100. However, in both cases, as in the case of using Sumikagel N-100,
It has not been possible to obtain a material that satisfies both water absorption stability and flame resistance.

[Effects of the Invention] As described above, in the fire extinguishing agent using the super absorbent resin according to the present invention, since phosphorus other than yellow phosphorus is added, it has unique excellent cooling effect, air blocking effect, water While maintaining the water absorption stability of super absorbent resin that has a loss prevention effect, it also has flame retardant properties.
In the event of a fire, it simultaneously exhibits both fire extinguishing power with excellent flame retardant properties and water damage prevention effect.

Further, in the above, when urea is further added, the amount of expensive phosphorus used can be reduced without reducing the water absorption stability of the super absorbent resin.

Claims (1)

[Claims] 1. A fire extinguishing agent prepared by adding a super absorbent resin and phosphorus excluding yellow phosphorus to water. 2. The fire extinguishing agent according to claim 1, wherein the super absorbent resin has a water absorption coefficient (weight after water absorption/weight before water absorption) of 500 or more. 3 Super absorbent resin is 0.1 to 2 parts by weight per 100 parts by weight of water.
The extinguishing agent according to claim 1, which is added in parts by weight. 4 Phosphorus, excluding yellow phosphorus, is 0.1 per 100 parts by weight of water.
The extinguishing agent according to claim 1, wherein ~1 part by weight is added. 5. A fire extinguishing agent made by adding super absorbent resin, phosphorus except yellow phosphorus, and urea to water. 6. The fire extinguishing agent according to claim 5, wherein the super absorbent resin has a water absorption coefficient (weight after water absorption/weight before water absorption) of 500 or more. 7 Super absorbent resin: 0.1 to 2 parts by weight per 100 parts by weight of water
The extinguishing agent according to claim 5, which is added in parts by weight. 8 Phosphorus, excluding yellow phosphorus, is 0.1 per 100 parts by weight of water.
The fire extinguishing agent according to claim 5, wherein ~1 part by weight is added.