JP2023133405A5

JP2023133405A5 - Self-extinguishing molded products

Info

Publication number: JP2023133405A5
Application number: JP2023118952A
Authority: JP
Filing date: 2023-07-21
Publication date: 2024-11-15

Description

以上、本発明の代表的な自己消火性成形品について説明したが、これらは全て上記の消火剤組成物を含んでいることから、火災発生時に火災の熱エネルギーを用いて消火機能を有する化学種を発生させることにより自己消火機能を発動することができ（図１のＸ部分）、火消火器や消火装置等を使用せずとも火災に対する安全対策が可能である。
Representative self- extinguishing molded articles of the present invention have been described above. Since all of these contain the above-mentioned fire extinguishing composition, when a fire occurs, the heat energy of the fire is used to generate chemical species having a fire extinguishing function, thereby activating the self-extinguishing function (part X in FIG. 1 ), and thus fire safety measures can be taken without using a fire extinguisher or fire extinguishing device.

≪実験例１≫（シート状）
＜実施例１～１３並びに比較例１～４＞
表１に示すＡ成分、Ｂ成分及びＣ成分を表１に示す配合割合（水分を含まない乾燥物として）十分混合し、Ａ成分、Ｂ成分及びＣ成分の合計量１００質量部に対して、１０質量
部相当のイオン交換水を添加してさらに混合した。得られた水湿混合品を１１０℃×１６時間の恒温槽にて乾燥させて、水分１質量％以下の乾燥品にした。
次に、乾燥品をメノウ乳鉢にて破砕して５００μｍ以下の粒径になるように整粒して粉砕物を得、粉砕物にＣＭＣを添加して粘土状の混合物を得、この混合物を厚さ５ｍｍのシート状に成形し、十分に乾燥させて本発明の自己消火性成形品１～９並びに比較自己消火性成形品１、３及び４を作製した。
<Experimental Example 1> (Sheet type)
<Examples 1 to 13 and Comparative Examples 1 to 4>
Components A, B, and C shown in Table 1 were thoroughly mixed in the proportions shown in Table 1 (as dry products not containing moisture), and 10 parts by mass of ion-exchanged water was added to 100 parts by mass of the total amount of components A, B, and C. The resulting water-wet mixture was dried in a thermostatic chamber at 110°C for 16 hours to give a dry product with a moisture content of 1% by mass or less.
Next, the dried product was crushed in an agate mortar and sized to a particle size of 500 μm or less to obtain a pulverized product. CMC was added to the pulverized product to obtain a clay-like mixture. This mixture was molded into a sheet having a thickness of 5 mm and thoroughly dried to produce self- extinguishing molded products 1 to 9 of the present invention and comparative self- extinguishing molded products 1, 3 and 4.

［評価試験］
（１）みかけ密度
上記のようにして得た自己消火性成形品のみかけ密度を、面積と厚さをデジタルノギスで測定し、測定値から求めた体積で重量を割ることにより求め、表１に記載した。
（２）消火試験
図５に示す装置にて消火試験１を実施した。
支持台５１の上に鉄製の金網５２を置き、その中心部に実施例および比較例の成形品５６を置いた。金網５２の上には、耐熱ガラス製の透明容器（５Ｌ）を被せて、金網５２に面している部分以外は密閉した。金網５２を介して成形品６の直下には、着火剤としてｎ－ヘプタン１００ｍｌを入れた皿５５を置いた。この状態にてｎ－ヘプタンを着火して火炎５７を生じさせ、成形品５６を熱してエアロゾルを発生させ、炎５７が消火できるかどうかを観察した。結果を表１に示した。
[Evaluation test]
(1) Apparent Density The apparent density of the self- extinguishing molded article obtained as described above was calculated by measuring the area and thickness with a digital caliper and dividing the weight by the volume calculated from the measured values. The results are shown in Table 1.
(2) Fire Extinguishing Test Fire extinguishing test 1 was carried out using the apparatus shown in FIG.
An iron wire mesh 52 was placed on a support stand 51, and a molded product 56 of the example and comparative example was placed in the center of the wire mesh 52. A transparent container (5 L) made of heat-resistant glass was placed on top of the wire mesh 52, and the container was sealed except for the part facing the wire mesh 52. A dish 55 containing 100 ml of n-heptane as an ignition agent was placed directly below the molded product 6 through the wire mesh 52. In this state, the n-heptane was ignited to generate a flame 57, and the molded product 56 was heated to generate an aerosol, and it was observed whether the flame 57 could be extinguished. The results are shown in Table 1.

≪実験例２≫（膜状）
＜実施例１４～２６並びに比較例５～８＞
実験例１と同様にして１００μｍ以下の粒径になるように整粒して粉砕物に、十分な量のＣＭＣを添加し、実験例１と比べて著しく粘度が低い分散液状の混合物を得た。この混合物を噴霧器に注入し、ガラス基板上に噴霧し、十分に乾燥させて厚さ３００μｍの膜状の本発明の自己消火性成形品１４～２６並びに比較自己消火性成形品５～８を作製した。
これらについて、実験例１と同様の消火試験を行ったところ、同様の結果が得られた。
Experimental Example 2 (film form)
<Examples 14 to 26 and Comparative Examples 5 to 8>
In the same manner as in Experimental Example 1, the particles were sized to a particle size of 100 μm or less, and a sufficient amount of CMC was added to the pulverized material to obtain a dispersion-like mixture with a significantly lower viscosity than that of Experimental Example 1. This mixture was poured into a sprayer, sprayed onto a glass substrate, and thoroughly dried to produce self- extinguishing molded articles 14 to 26 of the present invention and comparative self- extinguishing molded articles 5 to 8 in the form of a film having a thickness of 300 μm.
When these were subjected to a fire extinguishing test similar to that in Experimental Example 1, similar results were obtained.

≪実験例３≫（ペレット状）
＜実施例２７及び比較例９＞
実験例１の実施例１と同様にして作成した粉砕物を、粉砕品２．０ｇを内径９．６ｍｍの所定の金型（臼）に充填し、杵を挿入の上、油圧ポンプで面圧２２０．５ＭＰａ（２２５０ｋｇ／ｃｍ^２）にて、５秒ずつ両面より加圧して、ペレット状の本発明の自己消火性成形品２７を得た。また、同サイズの木材ペレットを比較成形品９とした。
これらについて、実験例１と同様の消火試験を行ったところ、自己消火性成形品２７については消火し、比較成形品９については消火しなかった。
また、比較成形品９に自己消火性成形品２７を混合して得た混合物について、同様の消火試験を行ったところ、自己消火性成形品２７の割合が多いほど消火の効果が著しかった。つまり、自己消火性成形品２７の割合が少ないほど、消火に時間を要し、また、消火できない場合もあった。
<Experimental Example 3> (Pellet form)
<Example 27 and Comparative Example 9>
The pulverized material prepared in the same manner as in Example 1 of Experimental Example 1 was filled in a predetermined die (mortar) with an inner diameter of 9.6 mm (2.0 g), a punch was inserted, and pressure was applied from both sides for 5 seconds each at a surface pressure of 220.5 MPa (2250 kg/ ^cm2 ) using a hydraulic pump to obtain a pellet-shaped self- extinguishing molded product 27 of the present invention. Wood pellets of the same size were used as comparative molded product 9.
When a fire extinguishing test was carried out on these in the same manner as in Experimental Example 1, the self- extinguishing molded product 27 extinguished the fire, whereas the comparative molded product 9 did not extinguish the fire.
In addition, a similar fire extinguishing test was carried out on a mixture obtained by mixing the comparative molded product 9 with the self- extinguishing molded product 27. The greater the proportion of the self- extinguishing molded product 27, the greater the fire extinguishing effect. In other words, the smaller the proportion of the self- extinguishing molded product 27, the longer it took to extinguish the fire, and in some cases the fire could not be extinguished at all.

表１から、本発明の実施例の自己消火性成形品では、いずれも瞬時に消火できた。比較例では、一時的に火勢は小さくなったが、消火はできなかった。
As can be seen from Table 1, the self- extinguishing molded articles of the examples of the present invention were able to instantly extinguish the fire, while the comparative examples were able to temporarily reduce the intensity of the fire but were unable to extinguish the fire.

ただし、本発明は、上記のシート状、膜状、柱状の自己消火性成形品に限られるものではなく、様々な応用が可能であり、また、建物の壁以外の種々の貼付物や柱以外の成形品にも適用可能である。例えば、種々の樹脂製品や木材製品にも適用可能である。
However, the present invention is not limited to the above-mentioned sheet-shaped, film-shaped, and column-shaped self- extinguishing molded products, and can be used in a variety of applications, including various attachments other than the walls of buildings and molded products other than columns, for example, various resin products and wood products.

本発明の形態を挙げれば以下のとおりである。
（１）燃焼によりエアロゾルを発生して火災を消火抑制する消火剤組成物を含むこと、を特徴とする自己消火性成形品。
（２）前記成形品が、平面状又は立体状であること、を特徴とする（１）に記載の自己消火性成形品。
（３）前記消火剤組成物が
燃料２０～５０質量％及び塩素酸塩８０～５０質量％を含有し、
更に前記燃料及び前記塩素酸塩の合計量１００質量部に対して、６～１０００質量部のカリウム塩を含有し、
熱分解開始温度が９０℃超～２６０℃の範囲であること、
を特徴とする（１）又は（２）に記載の自己消火性成形品。
（４）前記カリウム塩の、１０度毎分昇温のＤＳＣ（示差走査熱量測定）分析において１００℃から４４０℃の間で発現した吸熱ピーク総量が、１００Ｊ／ｇから９００Ｊ／ｇであること、
を特徴とする（１）～（３）のうちのいずれかに記載の自己消火性成形品。
（５）前記カリウム塩が熱エネルギーによりカリウムラジカルを発生する化合物であること、
を特徴とする（１）～（４）のうちのいずれかに記載の自己消火性成形品。
（６）前記カリウム塩が、酢酸カリウム、プロピオン酸カリウム、クエン酸一カリウム、クエン酸二カリウム、クエン酸三カリウム、エチレンジアミン四酢酸三水素一カリウム、エチレンジアミン四酢酸二水素二カリウム、エチレンジアミン四酢酸一水素三カリウム、エチレンジアミン四酢酸四カリウム、フタル酸水素カリウム、フタル酸二カリウム、シュウ酸水素カリウム、シュウ酸二カリウム及び重炭酸カリウムのうちの少なくとも１種であること、
を特徴とする（１）～（５）のうちのいずれかに記載の自己消火性成形品。
（７）前記燃料が前記塩素酸塩とともに燃焼して熱エネルギーを発生する化合物であること、を特徴とする（１）～（６）のうちのいずれかに記載の自己消火性成形品。
（８）前記燃料が、ジシアンジアミド、ニトログアニジン、硝酸グアニジン、尿素、メラミン、メラミンシアヌレート、アビセル、グアガム、カルボキシルメチルセルロースナトリウム、カルボキシルメチルセルロースカリウム、カルボキシルメチルセルロースアンモニウム、ニトロセルロース、アルミニウム、ホウ素、マグネシウム、マグナリウム、ジルコニウム、チタン、水素化チタン、タングステン及びケイ素のうちの少なくとも１種であること、
を特徴とする（７）記載の自己消火性成形品。
（９）前記塩素酸塩が、前記燃料とともに燃焼して熱エネルギーを発生する酸化剤化合物であること、を特徴とする（１）～（８）のうちのいずれかに記載の自己消火性成形品。
（１０）前記塩素酸塩が、塩素酸カリウム、塩素酸ナトリウム、塩素酸ストロンチウム、塩素酸アンモニウム及び塩素酸マグネシウムのうちの少なくとも１種であること、を特徴とする（９）記載の自己消火性成形品。
The embodiments of the present invention are as follows.
(1) A self-extinguishing molded article, comprising a fire extinguishing composition that generates an aerosol upon combustion to extinguish and suppress a fire.
(2) The self-extinguishing molded article according to (1), characterized in that the molded article is flat or three-dimensional.
(3) The extinguishing composition contains 20 to 50% by mass of a fuel and 80 to 50% by mass of a chlorate,
Further, the fuel and the chlorate salt are mixed together to obtain a mixture of 6 to 1,000 parts by mass of a potassium salt, based on 100 parts by mass of the total amount of the fuel and the chlorate salt.
The thermal decomposition starting temperature is in the range of more than 90°C to 260°C;
The self-extinguishing molded article according to (1) or (2),
(4) In a DSC (differential scanning calorimetry) analysis of the potassium salt at a temperature rise rate of 10 degrees per minute, the total amount of endothermic peaks appearing between 100°C and 440°C is 100 J/g to 900 J/g;
The self-extinguishing molded article according to any one of (1) to (3),
(5) The potassium salt is a compound that generates potassium radicals by thermal energy.
The self-extinguishing molded article according to any one of (1) to (4),
(6) The potassium salt is at least one of potassium acetate, potassium propionate, monopotassium citrate, dipotassium citrate, tripotassium citrate, monopotassium trihydrogen ethylenediaminetetraacetate, dipotassium dihydrogen ethylenediaminetetraacetate, tripotassium monohydrogen ethylenediaminetetraacetate, tetrapotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, dipotassium phthalate, potassium hydrogen oxalate, dipotassium oxalate, and potassium bicarbonate;
The self-extinguishing molded article according to any one of (1) to (5),
(7) The self-extinguishing molded article according to any one of (1) to (6), characterized in that the fuel is a compound that burns together with the chlorate to generate thermal energy.
(8) The fuel is at least one of dicyandiamide, nitroguanidine, guanidine nitrate, urea, melamine, melamine cyanurate, Avicel, guar gum, sodium carboxymethylcellulose, potassium carboxymethylcellulose, ammonium carboxymethylcellulose, nitrocellulose, aluminum, boron, magnesium, magnalium, zirconium, titanium, titanium hydride, tungsten, and silicon;
The self-extinguishing molded article according to (7) above,
(9) The self-extinguishing molded article according to any one of (1) to (8), wherein the chlorate is an oxidizer compound that burns together with the fuel to generate thermal energy.
(10) The self-extinguishing molded article according to (9), characterized in that the chlorate is at least one of potassium chlorate, sodium chlorate, strontium chlorate, ammonium chlorate and magnesium chlorate.

１、１１、２１、３１・・・自己消火性成形品、
２、１２・・・被貼付物、
２１ａ、３１ａ・・・消火剤組成物。
1, 11, 21, 31... Self- extinguishing molded product,
2, 12 ... object to be attached,
21a, 31a...Fire extinguishing composition.

Claims

Potassium chlorate,
one or more potassium salts selected from the group consisting of potassium acetate, potassium propionate, tripotassium citrate, tripotassium ethylenediaminetetraacetate, potassium hydrogen phthalate, potassium oxalate, and potassium bicarbonate;
and a component (component A) that, when burned, decomposes the potassium salt together with the potassium chlorate to generate an aerosol containing potassium radicals,
The self-extinguishing molded article contains the potassium chlorate and the component A in proportions of 80 to 50 mass % and 20 to 50 mass %, respectively, relative to the total amount of the potassium chlorate and the component A, and contains the potassium salt in a proportion of 6 to 1,000 parts by mass relative to 100 parts by mass of the total amount of the potassium chlorate and the component A.

The self-extinguishing molded article according to claim 1 , which is in the form of a sheet.