JP2012236962A - Flame-retardant and unburnable eva resin material and flame-retardant and unburnable product using the same - Google Patents

Flame-retardant and unburnable eva resin material and flame-retardant and unburnable product using the same Download PDF

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JP2012236962A
JP2012236962A JP2011153250A JP2011153250A JP2012236962A JP 2012236962 A JP2012236962 A JP 2012236962A JP 2011153250 A JP2011153250 A JP 2011153250A JP 2011153250 A JP2011153250 A JP 2011153250A JP 2012236962 A JP2012236962 A JP 2012236962A
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flame
retardant
resin
unburnable
sodium polyborate
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Takeshi Ozaki
健 尾崎
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TRUST LIFE KK
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Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant and unburnable EVA resin material, wherein sodium polyborate is prevented from being foamed during a production process; and to provide flame-retardant and unburnable products using the same.SOLUTION: The flame-retardant and unburnable EVA resin material is characterized in that powder consisting of the sodium polyborate is mixed in a mass ratio of 5 to 200% to an ethylene-vinyl acetate copolymer resin having a melting point of 95°C or lower.

Description

本発明は、難燃性又は不燃性を付与した樹脂材料及びそれを用いた難燃・不燃性製品に関する。   The present invention relates to a resin material imparted with flame retardancy or incombustibility and a flame retardant / incombustible product using the same.

樹脂材料に難燃性、不燃性を付与するのにポリホウ酸ナトリウムを混合する技術が特許文献1に開示されている。
しかし、同公報に開示する実施例は、塩化ビニルにポリホウ酸ナトリウムを150〜160℃にて混練するものであり、この温度範囲では、ポリホウ酸ナトリウムが少なくとも部分的に発泡化し、均一に分散しなかったりして製品化が困難であった。
また、塩化ビニルのような水素結合のできる極性基の少ない樹脂ではポリホウ酸ナトリウムとの密着混合性が不充分であった。
一方、エチレン−酢酸ビニル共重合樹脂(EVA樹脂:ethylene−vinylacetate copolymer)は、高密度ポリエチレンと比較して、弾力性、強靭性、透明性が高く、酢酸ビニルの配合割合が高くなるにつれて、結晶性が低下し、柔軟性が増すと共に、融点が低くなる。
また、樹脂中のアセチル基とポリホウ酸ナトリウムとの水素結合が強く作用する。
そこで、本発明者はこの樹脂を用いて難燃・不燃化することを検討し、本発明に至った。
Patent Document 1 discloses a technique of mixing sodium polyborate to impart flame retardancy and nonflammability to a resin material.
However, in the examples disclosed in the publication, sodium polyborate is kneaded with vinyl chloride at 150 to 160 ° C., and at this temperature range, sodium polyborate is at least partially foamed and uniformly dispersed. It was difficult to make a product.
Further, a resin having few polar groups capable of hydrogen bonding such as vinyl chloride has insufficient adhesion and mixing properties with sodium polyborate.
On the other hand, ethylene-vinyl acetate copolymer resin (EVA resin: ethylene-vinylacetate copolymer) has higher elasticity, toughness, and transparency as compared with high-density polyethylene, and as the proportion of vinyl acetate increases, The properties decrease, the flexibility increases, and the melting point decreases.
Moreover, the hydrogen bond between the acetyl group in the resin and sodium polyborate acts strongly.
Then, this inventor examined making it flame-retardant and incombustible using this resin, and came to this invention.

特開2010−24281号公報JP 2010-24281 A

本発明は製造工程において、ポリホウ酸ナトリウムの発泡化を抑えた難燃・不燃化EVA樹脂材料及びそれを用いた難燃・不燃性製品の提供を目的とする。   An object of the present invention is to provide a flame retardant / non-flammable EVA resin material in which foaming of sodium polyborate is suppressed in a production process and a flame retardant / non-flammable product using the same.

本発明に係る難燃・不燃性樹脂材料は、融点95℃以下のエチレン−酢酸ビニル共重合樹脂(以下、必要に応じてEVA樹脂と称する)に、当該EVA樹脂に対して質量比で5〜200%のポリホウ酸ナトリウムの粉末を混合したことを特徴とする。
ポリホウ酸ナトリウムのEVA樹脂に対する混合比は要求される難燃性、不燃性に応じて設定されるが、質量比で5%未満だと難燃性の効果が十分に現れない。
ポリホウ酸ナトリウムはEVA樹脂との水素結合により親和性が高いものの、ポリホウ酸ナトリウムの嵩比重はEVA樹脂の約半分である。
本発明者の実験によれば、EVA樹脂の質量に対して200%まで多量に混合できた。
ポリホウ酸ナトリウムの混合量が多い程不燃性が向上するが、実用的には5〜100%の範囲であり高い不燃性が要求される場合は20%以上がよい。
従って、より好ましい範囲は20〜80%である。
EVA樹脂は、酢酸ビニル(以下、必要に応じてVAと称する)の配合割合が多いほど融点が低くなる。
例えば、EVA樹脂中にVAを質量で10%になるように混合した場合に融点が94℃であり、VAの割合が33%のときの融点は61℃である。
従って、ポリホウ酸ナトリウムの発泡化を抑えつつ、EVA樹脂とポリホウ酸ナトリウム粉末との混練工程、樹脂製品の生産工程等の生産性を考えるとEVA樹脂の溶融温度は低い方が良く、融点を80℃未満に抑えるとさらに良い。
EVA樹脂中のVAの割合は、3〜45%の範囲で使用できるが、EVA樹脂の融点を95℃以下に設定するには、10〜45%の範囲であり、好ましくは10〜40%であり、さらに好ましくは20〜40%の範囲である。
また、混合方法としてはEVA樹脂を溶融させた状態に粉末状のポリホウ酸ナトリウムを添加混合してもよく、ペレット状又は粉末状のEVA樹脂と粉末状のポリホウ酸ナトリウムを撹拌混合し、定法に従い、押出や延伸により、シート材、フイルム材、あるいは金型を用いて充填、射出成形しても良い。
ここでポリホウ酸ナトリウムの粉末の製造として厚みのあるシート材や成形品の場合には、ポリホウ酸ナトリウム溶液を噴霧乾燥させた平均粒径10〜30μmの粉末を用いることができ、薄い厚み1mm以下のフイルム材を製造するには、ジェットミル等で平均粒径10μm以下、例えば、1〜5μmの微粉末にして用いるのが好ましい。
ここで、難燃性とは、材料に火炎を当てると火が付くがこの火炎を遠ざけるとすぐに自己消火するものをいい、規格としては例えば、米国の「Underwriter’s Laboratoies, Inc.」が制定した94V(Vertical testing),94VTM(Vertical testing for Thin Materials)をクリアーする場合をいう。
規格94Vの内容をさらに詳しく説明すると、難燃性の高い順に5VA,5VB,V−0,V−1,V−2,HBの等級に区分されている。
5VAと5VBは垂直に保持した短冊状の試料の下端に5秒間ガスバーナーの炎を接炎させた後に5秒間離す操作を5回繰り返し、最後の接炎の後、60秒以上燃焼を続けることがなく、試料の下方に置かれた脱脂綿を発火させる燃焼粒子の落下がないことをいう。
この試験をクリアーしたもののうち、板状試料を水平にしてガスバーナーの炎を接炎し、試料に穴が開かないものを5VA,穴が開く場合を5VBという。
V−0,V−1,V−2は垂直に保持した短冊状の試料の下端に10秒間ガスバーナーの炎を接炎させ燃焼が30秒以内に止まったならば、さらに接炎させる。
この試験により、接炎の後に燃焼を続ける時間、5個の試料の合計10回の接炎に対する総燃焼時間、試料の下方に置かれた脱脂綿の発火の有無等にて等級が区分されている。
不燃性とは火炎を当てても着火しないことをいい、規格としては例えば、JIS A 1323 A種〜C種の試験をクリアーすることをいう。
本発明に係る難燃・不燃性樹脂材料はそのまま、シート材、フイルム材、成形材等として製品化できるが、メッシュ生地、布生地、紙生地、紐、ロープ材等と組合せて製品化しても良い。
その場合に、融点95℃以下のエチレン−酢酸ビニル共重合樹脂に、質量比で5〜200%のポリホウ酸ナトリウムの粉末を混合した樹脂組成物を生地材にコーティング又は含浸させても、エチレン−酢酸ビニル共重合エマルジョン溶液に、ポリホウ酸ナトリウムの粉末又は、ポリホウ酸ナトリウムの溶液を混合した混合液を、生地材にコーティング又は含浸させた後に乾燥させても良い。
この場合も要求される難燃性、不燃性に応じてポリホウ酸ナトリウムの配合量を設定することになる。
ポリホウ酸ナトリウムは、ホウ酸、ホウ砂を原料にして、ホウ酸又はホウ砂単独の溶解度(20℃)以上に濃度を高くした水溶液であり、例えば、本出願人は、商品名ファイアレスBリキッドを販売していて、これを用いて噴霧乾燥や凍結乾燥を経て、粉末化できる。
また、特開2005−112700号に記載の製造方法を取り込むことができる。
EVAエマルジョンにポリホウ酸ナトリウム溶液を加えるには、固形分が30%以上になるように予め高濃度にするのが良い。
本発明に係る樹脂材料は、EVA樹脂とポリホウ酸ナトリウムの他に水酸化アルミニウム又は水酸化マグネシウムの粉末を混合してもよい。
この場合に水酸化アルミニウム、水酸化マグネシウムの混合割合はポリホウ酸ナトリウムに対する質量比で5〜50%の範囲がよい。
また、ねばねば感を取るために炭酸カルシウムの粉末をEVA樹脂に対する質量比で0.1〜30%、好ましくは1.0〜10%混合してもよい。
さらにはEVA樹脂との混練性を向上させるために界面活性剤等の分散剤をEVA樹脂に対する質量比で0.1〜10%、好ましくは1.0〜10%添加してもよい。
本発明に係る樹脂材料は、タングステン、鉛等の放射線を遮蔽する作用を有する金属の粉末を混合すると、難燃・不燃放射線遮蔽材料となる。
この材料をそのままシートやフィルム状にしてもよいが、引張強度を強くするために難燃、不燃化した綿生地やその他の繊維生地を芯材に用いてもよい。
また、不燃性向上を目的にアルミ箔、ガラス繊維シート等を積層してもよい。
本発明に係る樹脂材料は、EVA樹脂をベースとしているので接着剤にも適用できる。
接着剤は溶着タイプでも溶液タイプにしてもよく、ポリホウ酸ナトリウムを混合することで不燃接着剤として使用することができる。
The flame retardant / incombustible resin material according to the present invention is an ethylene-vinyl acetate copolymer resin having a melting point of 95 ° C. or less (hereinafter referred to as EVA resin as necessary) in a mass ratio of 5 to 5 with respect to the EVA resin. 200% sodium polyborate powder is mixed.
The mixing ratio of sodium polyborate to EVA resin is set according to the required flame retardancy and non-flammability, but if the mass ratio is less than 5%, the flame retardancy effect does not sufficiently appear.
Although sodium polyborate has a high affinity due to hydrogen bonding with EVA resin, the bulk specific gravity of sodium polyborate is about half that of EVA resin.
According to the experiment of the present inventor, it was possible to mix in a large amount up to 200% with respect to the mass of the EVA resin.
The greater the amount of sodium polyborate mixed, the better the incombustibility. However, it is practically in the range of 5 to 100%, and when high incombustibility is required, 20% or more is preferable.
Therefore, a more preferable range is 20 to 80%.
The EVA resin has a lower melting point as the blending ratio of vinyl acetate (hereinafter referred to as VA as necessary) increases.
For example, when VA is mixed in EVA resin so as to have a mass of 10%, the melting point is 94 ° C., and the melting point when the ratio of VA is 33% is 61 ° C.
Therefore, considering the productivity of the kneading process of EVA resin and sodium polyborate powder, the production process of the resin product, etc. while suppressing the foaming of sodium polyborate, the melting temperature of EVA resin should be low, and the melting point should be 80 It is even better if it is kept below ℃.
The proportion of VA in the EVA resin can be used in the range of 3 to 45%, but in order to set the melting point of the EVA resin to 95 ° C. or less, it is in the range of 10 to 45%, preferably 10 to 40%. Yes, more preferably in the range of 20-40%.
In addition, as a mixing method, powdered sodium polyborate may be added and mixed in a state in which EVA resin is melted, and pelletized or powdered EVA resin and powdered sodium polyborate are stirred and mixed according to a conventional method. Alternatively, filling or injection molding may be performed by extrusion or stretching using a sheet material, a film material, or a mold.
Here, in the case of a thick sheet material or molded product for the production of sodium polyborate powder, a powder having an average particle diameter of 10 to 30 μm obtained by spray drying a sodium polyborate solution can be used, and a thin thickness of 1 mm or less. In order to produce the film material, it is preferable to use a fine powder having an average particle size of 10 μm or less, for example, 1 to 5 μm, by a jet mill or the like.
Here, “flame retardant” refers to a material that is ignited when it is exposed to a flame, but self-extinguishes as soon as the flame is moved away. This refers to the case of clearing the established 94V (Vertical Testing) and 94VTM (Vertical Testing for Thin Materials).
The contents of the standard 94V will be described in more detail. The grades are classified into 5VA, 5VB, V-0, V-1, V-2, and HB in descending order of flame retardancy.
For 5VA and 5VB, the gas burner flame is in contact with the lower end of the strip-shaped sample held vertically for 5 seconds and then released for 5 seconds. After the last flame contact, the combustion continues for 60 seconds or more. This means that there is no falling of burning particles that ignite absorbent cotton placed under the sample.
Of those that have cleared this test, the plate-like sample is placed horizontally and the flame of the gas burner is in contact with the sample.
For V-0, V-1, and V-2, the flame of the gas burner is brought into contact with the lower end of the strip-like sample held vertically for 10 seconds, and if the combustion stops within 30 seconds, the flame is further brought into contact.
According to this test, the grades are classified according to the duration of burning after flame contact, the total burning time for a total of 10 flames of 5 samples, the presence or absence of ignition of absorbent cotton placed under the sample, etc. .
Non-flammability means that it does not ignite even when a flame is applied, and as a standard, for example, it means that a test of JIS A 1323 A type to C type is cleared.
The flame-retardant / non-flammable resin material according to the present invention can be commercialized as it is as a sheet material, a film material, a molding material, etc., but can be commercialized in combination with a mesh fabric, cloth fabric, paper fabric, string, rope material, good.
In that case, ethylene-vinyl acetate copolymer resin having a melting point of 95 ° C. or less and a resin composition obtained by mixing 5 to 200% by weight of sodium polyborate powder in mass ratio may be coated or impregnated on the fabric material. The dough material may be coated or impregnated with a mixture of a vinyl acetate copolymer emulsion solution mixed with sodium polyborate powder or sodium polyborate solution, and then dried.
Also in this case, the blending amount of sodium polyborate is set according to the required flame retardancy and nonflammability.
Sodium polyborate is an aqueous solution using boric acid or borax as a raw material and having a concentration higher than the solubility (20 ° C.) of boric acid or borax alone. Can be pulverized by spray drying or freeze drying.
Moreover, the manufacturing method of Unexamined-Japanese-Patent No. 2005-112700 can be taken in.
In order to add the sodium polyborate solution to the EVA emulsion, it is preferable to increase the concentration beforehand so that the solid content is 30% or more.
The resin material according to the present invention may be mixed with aluminum hydroxide or magnesium hydroxide powder in addition to EVA resin and sodium polyborate.
In this case, the mixing ratio of aluminum hydroxide and magnesium hydroxide is preferably in the range of 5 to 50% by mass ratio with respect to sodium polyborate.
Moreover, in order to take a sticky feeling, the powder of calcium carbonate may be mixed in an amount of 0.1 to 30%, preferably 1.0 to 10% by mass ratio with respect to the EVA resin.
Furthermore, in order to improve the kneadability with the EVA resin, a dispersant such as a surfactant may be added in an amount of 0.1 to 10%, preferably 1.0 to 10% by mass ratio with respect to the EVA resin.
The resin material according to the present invention becomes a flame retardant / incombustible radiation shielding material when mixed with a metal powder having an action of shielding radiation such as tungsten and lead.
This material may be used in the form of a sheet or film as it is, but in order to increase the tensile strength, a flame-retardant or incombustible cotton fabric or other fiber fabric may be used as the core material.
Moreover, you may laminate | stack aluminum foil, a glass fiber sheet, etc. for the purpose of nonflammability improvement.
Since the resin material according to the present invention is based on EVA resin, it can also be applied to an adhesive.
The adhesive may be a weld type or a solution type, and can be used as a nonflammable adhesive by mixing sodium polyborate.

ポリホウ酸ナトリウムは150℃以上になると一部が発泡化する性質を有しているために一般的な熱可塑性樹脂ではポリホウ酸ナトリウムの粉末を混練する工程にて発泡し、製品化できなかった。
これに対して、本発明に係るEVA樹脂は混練や押出成形温度が120℃以下、さらには、100℃以下なのでポリホウ酸ナトリウムの発泡化を抑えることができる。
Since sodium polyborate has a property of partially foaming at 150 ° C. or higher, a general thermoplastic resin foams in a step of kneading sodium polyborate powder and cannot be commercialized.
On the other hand, since the EVA resin according to the present invention has a kneading or extrusion temperature of 120 ° C. or lower, and further 100 ° C. or lower, it is possible to suppress foaming of sodium polyborate.

火災による燃焼試験を実施した結果を示す。The result of the fire combustion test is shown. JIS A 1323に基づく難燃性試験結果を示す。The flame retardance test result based on JIS A 1323 is shown. メッシュ生地材を難燃・不燃化する例を示す。An example of flame retardant / incombustible mesh fabric material is shown. ロープ材を難燃・不燃化する例を示す。An example of making the rope material incombustible and incombustible is shown.

本発明に係る難燃樹脂材料の製造例について説明する。
酢酸ビニルの含有量が33%のEVA樹脂(融点61℃)に対して質量比で20%の量のポリホウ酸ナトリウム粉末を溶融樹脂に混練し、シート状に押出成形したサンプルに1300℃のバーナー火炎を図1のA部に当てた。
その結果、周囲に白色化した発泡部分が認められ、図1(b)に示した裏面には影響が無く不燃化されていた。
これにより、上記94V、94VTM規格を十分にクリアーしていることが推定される。
また、3×3mmの大きさの角に細切りした試料3.3gをJIS K 2541−3に基づいて燃焼管空気法による試験をした結果、塩素もケイ素も検出されなかった。
現在、原子力発電所で使用されている不燃性シートはガラス繊維をシリコンコーティングした厚み約2.5mmのシート材である。
しかし、現在の上記不燃性シート材は焼却できず、そのままドラム缶に詰めて、六ヶ所村施設に搬送されていて、かさ高であり、処理費用が高額になるが、本発明に係る不燃樹脂材料を用いれば、焼却に有害なガス発生が無く、焼却減量化して搬送することで、処理費の低コスト化を図ることができる。
次に酢酸ビニルの含有量が33%のEVA樹脂に対して質量比で50%のポリホウ酸ナトリウムの粉末を混練し、シート状に押出成形したサンプルを用いて94V試験を実施したところ、5VA,5VBの等級をクリアーした。
Production examples of the flame-retardant resin material according to the present invention will be described.
A 1300 ° C. burner is formed on a sample obtained by kneading sodium polyborate powder in an amount of 20% by mass with respect to an EVA resin (melting point: 61 ° C.) having a vinyl acetate content of 33% into a molten resin and extruding it into a sheet. The flame was applied to part A in FIG.
As a result, a whitened foamed portion was observed around the periphery, and the back surface shown in FIG.
As a result, it is estimated that the 94V and 94VTM standards are sufficiently cleared.
In addition, as a result of testing 3.3 g of a sample cut into 3 × 3 mm corners by a combustion tube air method based on JIS K2541-3, neither chlorine nor silicon was detected.
Currently, the non-combustible sheet used in nuclear power plants is a sheet material having a thickness of about 2.5 mm in which glass fibers are coated with silicon.
However, the present non-combustible sheet material cannot be incinerated, and is packed in a drum can as it is and transported to Rokkasho village facility, which is bulky and processing costs are high. If there is no gas generation harmful to incineration, the amount of incineration can be reduced and transported to reduce the processing cost.
Next, a 94V test was carried out using a sample obtained by kneading 50% by weight sodium polyborate powder with an EVA resin having a vinyl acetate content of 33% and extruding it into a sheet. The grade of 5VB was cleared.

例えば、シート材の強度アップを図るべく、ポリホウ酸ナトリウム水溶液を固形分の付着量が20〜50g/mになるようにスプレー又は浸漬及び乾燥した不燃性紙糸繊維を心材にし本発明に係る不燃性樹脂材料を用いてシート材を製造することができる。
図2に試作したシート材も用いて、JIS A 1323に基づく難燃性A種の試験をした結果を示し、(a)に試験表面側、(b)に裏面側を示すように、発炎は認められなかった。
For example, in order to increase the strength of the sheet material, the non-combustible paper yarn fiber sprayed or dipped and dried so that the solid content of the aqueous solution of sodium borate is 20 to 50 g / m 2 is used as a core material according to the present invention. A sheet material can be manufactured using a nonflammable resin material.
FIG. 2 shows the result of the test of flame retardant type A based on JIS A 1323 using the prototype sheet material, and (a) shows the test surface side, and (b) shows the back side. Was not recognized.

本発明に係る樹脂は、図3に示すようにメッシュ生地材1に樹脂シート2を重ね、加熱溶融し心材入りの不燃シート10を製造したり、図4に示すようにロープ材1aに不燃EVA樹脂1bを溶融含浸被覆することで難燃・不燃化することもできる。
用途に応じて、安定化剤、着色剤、滑剤との各種添加剤を配合してもよく、難燃性、不燃性が必要とされる全ての分野に適用できる。
例えば、不燃性テント、不燃性壁紙、不燃性建築内装材、不燃性車両内装材、配電工事に使用する防護シート(トラッキング防止)等、例を挙げると切りがない。
また、タングステンや鉛の粉末を混合すると放射線の遮蔽機能を付加することができる。
As shown in FIG. 3, the resin according to the present invention is obtained by superposing the resin sheet 2 on the mesh dough material 1 and heating and melting it to produce a non-combustible sheet 10 containing a core material, or as shown in FIG. Flame retardant / incombustible can also be achieved by melt impregnation coating with resin 1b.
Various additives such as stabilizers, colorants, and lubricants may be blended depending on the application, and can be applied to all fields where flame retardancy and incombustibility are required.
For example, non-combustible tents, non-combustible wallpaper, non-combustible building interior materials, non-combustible vehicle interior materials, protective sheets (anti-tracking) used for power distribution work, etc. are all the examples.
Further, when tungsten or lead powder is mixed, a radiation shielding function can be added.

Claims (3)

融点95℃以下のエチレン−酢酸ビニル共重合樹脂に、当該エチレン−酢酸ビニル共重合樹脂に対して質量比で5〜200%のポリホウ酸ナトリウムの粉末を混合したことを特徴とする難燃・不燃性樹脂材料。   Flame retardant / non-flammable characterized by mixing ethylene-vinyl acetate copolymer resin having a melting point of 95 ° C. or less with 5-200% sodium polyborate powder by mass ratio with respect to the ethylene-vinyl acetate copolymer resin Resin material. 融点95℃以下のエチレン−酢酸ビニル共重合樹脂に、当該エチレン−酢酸ビニル共重合樹脂に対して質量比で5〜200%のポリホウ酸ナトリウムの粉末を混合した樹脂組成物を生地材にコーティング又は含浸してあることを特徴とする難燃・不燃製品。   A dough material is coated with a resin composition obtained by mixing an ethylene-vinyl acetate copolymer resin having a melting point of 95 ° C. or less with 5-200% sodium polyborate powder in a mass ratio with respect to the ethylene-vinyl acetate copolymer resin. Flame retardant / non-flammable product characterized by impregnation. エチレン−酢酸ビニル共重合エマルジョン溶液に、ポリホウ酸ナトリウムの粉末又は、ポリホウ酸ナトリウムの溶液を混合した混合液を、生地材にコーティング又は含浸させた後に乾燥させることを特徴とする難燃・不燃性製品の製造方法。   Flame retardant and non-flammable, characterized in that a mixture of an ethylene-vinyl acetate copolymer emulsion solution mixed with sodium polyborate powder or sodium polyborate solution is coated or impregnated into a fabric material and then dried. Product manufacturing method.
JP2011153250A 2011-04-23 2011-07-11 Flame-retardant and unburnable eva resin material and flame-retardant and unburnable product using the same Withdrawn JP2012236962A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013018878A (en) * 2011-07-12 2013-01-31 Trust Life:Kk Nonflammable and radiation shielding sheet
JP2014111371A (en) * 2012-11-08 2014-06-19 Yoshda Fusa Orimono Kk Flame-retardant tabular object, toxic gas generation-inhibiting rug using flame-retardant tabular object, and method for manufacturing toxic gas generation-inhibiting rug

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013018878A (en) * 2011-07-12 2013-01-31 Trust Life:Kk Nonflammable and radiation shielding sheet
JP2014111371A (en) * 2012-11-08 2014-06-19 Yoshda Fusa Orimono Kk Flame-retardant tabular object, toxic gas generation-inhibiting rug using flame-retardant tabular object, and method for manufacturing toxic gas generation-inhibiting rug

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