JP4014480B2 - Aqueous flame retardant for wood and method for making wood flame retardant using the same - Google Patents
Aqueous flame retardant for wood and method for making wood flame retardant using the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、木材の難燃化に関し、詳しくは、耐水性にすぐれる難燃性を木材に付与し得る木材用水性難燃剤とそれを用いる木材の難燃化方法とそれを用いて得られる難燃化木材に関する。
【０００２】
【従来の技術】
従来、木材を難燃化するために、ハロゲン系難燃剤、ガラス系難燃剤、リン系難燃剤等を含む水性難燃剤を木材に塗布、含浸させる方法が知られている。しかしながら、ハロゲン系難燃剤を用いた場合には、木材が燃焼時に有害なガスを発生する問題がある。また、水性難燃剤は、耐水性に劣るので、木材に適用した後、溶出して、木材の難燃性が経時的に低下する問題もある。
【０００３】
そこで、ホウ酸トリエチルのような加水分解性の金属アルコキシドを木材に含浸させ、加水分解させて、木材内で不燃性の金属酸化物に変える方法や（特許文献１参照）、同様に、テトラエトキシシランやテトラエトキシチタン等の金属アルコキシドの溶液を木材に含浸させ、加水分解させて、木材の細胞空隙内で不燃性の金属酸化物を生成させる方法等が知られている（特許文献２を参照）。また、上記金属アルコキシドにアルカリ金属化合物又はアルカリ土類金属化合物を組み合わせた水性難燃剤を用いることも提案されている（特許文献３参照）。更に、リンやホウ素を含む特殊なメチルシロキサンオリゴマーを木材に含浸させる難燃化方法も知られている（特許文献５及び６参照）。
【０００４】
しかし、このように、金属アルコキシドを用いる難燃化処理においては、一般に、難燃剤を木材に減圧注入、加圧注入等の方法によって、木材中に注入、含浸させるので、例えば、刷毛塗りやスプレー塗布せざるを得ない文化財等の建築物をはじめ、一般の既存の建築物には適用し難い。更に、金属アルコキシド、特に、シランカップリング剤のみを難燃剤として木材に適用すると、残炎時間や残じん時間が長くなるので、難燃化が不十分である。しかも、一般に、金属アルコキシドは高価であるので、実用し難い問題がある。
【０００５】
水性難燃剤による木材の難燃性の耐水性を改善するために、難燃剤を木材に塗布し、乾燥させた後、その木材の表面にシリコーン樹脂からなる被覆層を形成させる方法も知られているが（特許文献４参照）、２段階の処理を必要とするうえに、依然として、処理費用が高く、実用性に難がある。
【０００６】
【特許文献１】
特開平０５−２７８００８号公報
【特許文献２】
特開２００２−１０３３０８号公報
【特許文献３】
特開２００１−２５２９０８号公報
【特許文献４】
特開平１１−１０５０１１号公報
【特許文献５】
特開平０９−０３８９１５号公報
【特許文献６】
特開平０９−３００３１２号公報
【０００７】
【発明が解決しようとする課題】
本発明は、木材の難燃化における上述した問題を解決するためになされたものであって、耐水性にすぐれる難燃性を木材に低廉に且つ容易に付与し得る水性難燃剤とそれを用いる木材の難燃化方法とそれを用いて得られる難燃化木材を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明によれば、
（Ａ）ホウ酸１モル部と尿素１〜５モル部とリン酸０．０５〜１モル部とを９０〜１６０℃の温度に加熱して得られる反応生成物からなる水性無機難燃剤及び（Ｂ）シランカップリング剤
をホウ素／ケイ素モル比２．５〜２０の範囲で含むことを特徴とする木材用水性難燃剤が提供される。また、本発明によれば、上記木材用水性難燃剤を木材に塗布、含浸させることを特徴とする木材の難燃化方法が提供される。更に、本発明によれば、上記木材用水性難燃剤で木材を処理してなる難燃化木材が提供される。
【０００９】
【発明の実施の形態】
本発明による木材用水性難燃剤は、
（Ａ）ホウ酸１モル部と尿素１〜５モル部とリン酸０．０５〜１モル部とを９０〜１６０℃、好ましくは、１００〜１４０℃の温度に加熱して得られる反応生成物からなる水性無機難燃剤及び
（Ｂ）シランカップリング剤
をホウ素／ケイ素モル比２．５〜２０の範囲で含むものである。
【００１０】
ホウ酸と尿素とリン酸とを加熱して、反応させる際に、ホウ酸１モル部に対して、１モル部より少ない量の尿素を用いるときは、得られる反応生成物の水溶性が低下するので好ましくない。他方、ホウ酸１モル部に対して、５モル部より多い量の尿素を用いるときは、得られる反応生成物をシランカップリング剤と組み合わせて難燃剤としたとき、十分な難燃性を木材に付与することができない。リン酸については、ホウ酸１モル部に対して、０．０５モル部より少ない量のリン酸を用いるときは、得られる反応生成物の難燃性が低下するので好ましくない。他方、ホウ酸１モル部に対して、１モル部より多い量のリン酸を用いるときは、得られる反応生成物の水溶性が低下して、シランカップリング剤と組合わせて難燃剤としたとき、十分な難燃性を木材に付与することができない。
【００１１】
ホウ酸と尿素とリン酸を加熱、反応させるには、通常、常圧下に１０〜９０分程度、加熱すればよい。必要に応じて、加熱下に加熱、反応させてもよい。また、ホウ酸と尿素とリン酸とを加熱、反応させる際に、反応溶剤として水や、水と少量の水溶性有機溶剤、例えば、アセトン、エーテル、メタノール、エタノール等との混合物を用いてもよい。従って、本発明による水性難燃剤は、少量のそのような水溶性有機溶剤を含んでいてもよい。
【００１２】
本発明によれば、このようにして、ホウ酸と尿素とリン酸とを加熱して、反応させ、得られた反応生成物に水を加え、水に溶解させて、水性無機難燃剤を得る。従って、本発明によれば、ホウ酸と尿素とリン酸とを加熱し、反応させて得られた反応生成物は水溶性である。そして、例えば、このようにして得られた水性無機難燃剤とシランカップリング剤との水溶液を混合すれば、本発明による木材用水性難燃剤を得ることができる。
【００１３】
本発明において、シランカップリング剤は、特に限定されるものではないが、しかし、好ましくは、例えば、一般式（Ｉ）
【００１４】
【化１】
（式中、Ｒ1 は反応性基又は反応性基を有するアルキル基を示し、Ｒ2 は炭素原子数１〜４のアルキル基を示し、Ｒ3 は炭素原子数１〜４のアルキル基を示し、ａ及びｂはそれぞれ独立に０、１又は２である。）
で表されるものが好ましく用いられる。
【００１６】
上記反応性基Ｒ1 としては、例えば、ビニル基を挙げることができ、また、反応性基を有するアルキル基としては、例えば、γ−グリシドキシプロピル基、γ−アクリロキシプロピル基、γ−メタクリロキシプロピル基、２−（３，４−エポキシシクロヘキシル）基等を挙げることができる。上記アルキル基Ｒ2 又はＲ3 としては、例えば、メチル基、エチル基、プロピル基又はブチル基を挙げることができ、炭素原子数３以上のアルキル基は直鎖状でも分岐鎖状でもよい。しかし、好ましくは、上記アルキル基Ｒ2 又はＲ3 はメチル基又はエチル基である。
【００１７】
従って、本発明において用いる好ましいシランカップリング剤として、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン等のテトラアルコキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリプロポキシシラン、エチルトリブトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリプロポキシシラン、プロピルトリブトキシシラン、ジメチルジエトキシシラン等のアルキルアルコキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等の反応性基を有するシランカップリング剤を挙げることができる。
【００１８】
なかでも、本発明によれば、光反応性基を有するシランカップリング剤、例えば、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン等が好ましく用いられる。
【００１９】
更に、本発明によれば、難燃剤は、従来より知られている薬剤を含んでいてもよい。そのような薬剤として、例えば、ホウ酸、ホウ砂、ホウ酸亜鉛、亜リン酸トリメチル、亜リン酸トリエチル、亜リン酸トリプロピル、亜リン酸トリブチル等の亜リン酸エステル、リン酸アンモニウム、硫酸アンモニウム、リン酸グアニジン、ホウ素やチタンのアルコキシド等を挙げることができる。但し、薬剤は、これら例示したものに限定されるものではない。
【００２０】
シランカップリング剤の水溶液は、好ましくは、シランカップリング剤の水への溶解を容易にするために、酢酸や木酢液を溶解助剤として含むことが好ましい。
【００２１】
本発明によれば、上述した木材用水性難燃剤を木材に塗布、含浸させた後、乾燥させることによって、木材を難燃化することができる。難燃剤を木材に塗布、含浸させるための手段、方法は特に限定されるものではなく、例えば、難燃化の対象が建築物の場合であれば、刷毛、スプレー、ロールコーター等を用いて塗布すればよい。難燃剤の木材への塗布量は、固形分換算で、通常、１０〜６０ｇ／ｍ2 程度であるが、しかし、これに限定されるものではない。他方、難燃化の対象が建築物に組み込まれる前の段階の材料であるときは、難燃剤を減圧注入や加圧注入によって木材に含浸させてもよい。
【００２２】
本発明によれば、水性難燃剤を木材に塗布、含浸させた後、乾燥させることによって、木材に難燃性を付与することができる。ここに、水性難燃剤を木材に塗布、含浸させた後、乾燥させるには、通常、常温で数日間、放置すればよいが、しかし、必要に応じて、加熱して、乾燥させてもよい。
【００２３】
特に、本発明に従って、難燃剤中のシランカップリング剤成分として、前述したような光反応性のシランカップリング剤を用いた場合には、難燃剤を木材に塗布、含浸させた後、紫外線を照射することによって、水性無機難燃剤の溶出を防いで、一層、耐水性にすぐれた難燃性を木材に付与することができる。このように、難燃剤中のシランカップリング剤成分として、光反応性のシランカップリング剤を用いることによって、水性無機難燃剤の溶出を防くことができる理由は、必ずしも明確ではなく、また、本発明は、そのような理由によっては何ら制約を受けるものではないが、光反応性のシランカップリング剤が光照射によって水性無機難燃剤中の成分と反応して、これを水不溶性とするからであるとみられる。
【００２４】
このようにして、木材に本発明による難燃剤を塗布、含浸させることによって、シランカップリング剤は木材中で加水分解し、縮合して、不燃性のケイ素酸化物からなるゲルを形成すると共に、上述したように、水性無機難燃剤の溶出を防ぐので、水性無機難燃剤と共に木材に耐水性ある難燃性を付与し、かくして、本発明による難燃化木材を得ることができる。
【００２５】
【実施例】
以下に実施例を挙げて本発明を説明するが、本発明はこれら実施例により何ら限定されるものではない。
【００２６】
実施例１
ホウ酸２モル、尿素４モル及びリン酸（８５重量％水溶液）０．２モルをセパラブルフラスコに仕込み、攪拌しながら、１１０℃まで昇温した後、この温度で１時間反応させて、実質的に粉状の反応生成物を得た。この反応生成物に水を加え、溶解させて、固形分３３重量％の水溶性無機難燃剤を得た。別に、６重量％酢酸水溶液５０ｇに攪拌下にγ−グリシドキシプロピルトリメトキシシラン５０ｇ（０．２モル）を添加し、酢酸水溶液中に溶解させて、シランカップリング剤水溶液を得た。そこで、上記水溶性無機難燃剤とシランカップリング剤水溶液とを混合して、ホウ素／シランカップリング剤のケイ素モル比が１０／１である本発明による水性難燃剤を得た。
【００２７】
この水性難燃剤を杉板（１１０ｍｍ×２９０ｍｍ、厚み１５ｍｍ、以下、同じ。）の表面に乾燥重量にて２０ｇ／ｍ2 の割合で塗布、含浸させた後、１週間、常温で放置し、乾燥させて、難燃性を評価するための初期試験片とした。別に、この初期試験片を水（３０℃）に３時間浸漬し、５０℃で１６時間乾燥させた後、常温まで放置して、難燃剤の耐水性を試験するための耐水性試験片とした。
【００２８】
実施例２
実施例１において、６重量％酢酸水溶液を一部、木酢液（１重量％）に置換した以外は、実施例１と同様にして、本発明による水性難燃剤を得、これを用いて、実施例１と同様にして、初期試験片と耐水性試験片とを調製した。
【００２９】
実施例３
実施例１において調製した水性難燃剤を杉板の表面に乾燥重量にて２０ｇ／ｍ2 の割合で塗布、含浸させた後、紫外線照射装置（ウシオ電機（株）製ＵＶＣ−１２１２）で紫外線を２０秒間照射して、初期試験片とした。別に、このように紫外線を照射して４時間後に試験片を水（３０℃）に３時間浸漬し、５０℃で１６時間乾燥させた後、常温まで放置して、難燃剤の耐水性を試験するための耐水性試験片とした。
【００３０】
実施例４
実施例１において、γ−グリシドキシプロピルトリメトキシシランに代えて、γ−メタクリロキシプロピルトリメトキシシランを用いた以外は、実施例１と同様にして、本発明による水性難燃剤を得、これを用いて、実施例１と同様にして、初期試験片と耐水性試験片とを調製した。
【００３１】
実施例５
実施例１において、水溶性無機難燃剤のホウ素／シランカップリング剤のケイ素モル比が１０／２となるように混合した以外は、実施例１と同様にして、水性難燃剤を調製し、これを用いて、初期試験片と耐水性試験片とを調製した。
【００３２】
実施例６
ホウ酸２モル、尿素８モル及びリン酸（８０重量％水溶液）１モルをセパラブルフラスコに仕込み、攪拌しながら、１１０℃まで昇温した後、この温度で１時間反応させて、実質的に粉状の反応生成物を得た。この反応生成物に水を加え、溶解させて、固形分３５重量％の水溶性無機難燃剤を得た。別に、６重量％酢酸水溶液５０ｇに攪拌下にγ−グリシドキシプロピルトリメトキシシラン５０ｇ（０．２モル）を添加し、酢酸水溶液中に溶解させて、シランカップリング剤水溶液を得た。
【００３３】
上記水溶性無機難燃剤５０重量部とシランカップリング剤水溶液１０重量部と４５重量％リン酸グアニジン水溶液５０重量部とを混合して、本発明による水性難燃剤を調製した。この水性難燃剤において、水溶性無機難燃剤のホウ素／シランカップリング剤のケイ素モル比は５であり、リン酸グアニジン固形分の割合は２０重量％であった。
【００３４】
この水性難燃剤を用いた以外は、実施例１と同様にして、初期試験片と耐水性試験片を調製した。
【００３５】
比較例１
杉板に何らの難燃処理も施すことなく、１週間、常温で放置し、乾燥させて、初期試験片とし、別に、この初期試験片を水（３０℃）に３時間浸漬し、５０℃で１６時間乾燥させた後、常温まで放冷して、耐水性試験片とした。
【００３６】
比較例２
実施例１において得られた水溶性無機難燃剤を杉板の表面に乾燥重量にて２０ｇ／ｍ2 の割合で塗布、含浸させた後、１週間、常温で放置し、乾燥させて、初期試験片とした。別に、この初期試験片を水（３０℃）に３時間浸漬し、５０℃で１６時間乾燥させた後、常温まで放置して、耐水性試験片とした。
【００３７】
比較例３
実施例１において、上記水溶性無機難燃剤の固形分／シランカップリング剤重量比が１０／５となるように混合した以外は、実施例１と同様にして、水性難燃剤を調製し、これを用いて、初期試験片と耐水性試験片とを調製した。
【００３８】
比較例４
リン酸グアニジン水溶液（５０重量％）を難燃剤として用いた以外は、実施例１と同様にして、初期試験片と耐水性試験片とを調製した。
【００３９】
比較例５
実施例１において調製したシランカップリング剤水溶液を杉板の表面に乾燥重量にて２０ｇ／ｍ2 の割合で塗布、含浸させた後、１週間、常温で放置し、乾燥させて、初期試験片とした。
【００４０】
上記実施例及び比較例で調製した初期試験片と耐水性試験片について、消防法４５度燃焼性試験に従って、消防法施行規則に定める「展示用合板」のメッケルバーナー法にて難燃性を試験した。結果を表１及び表２に示す。初期試験片の試験においては、残炎時間が１０秒以下、残じん時間が３０秒以下、多環面積が７０ｃｍ2 以下のときを合格とし、この基準に満たないときは不合格とした。耐水性試験片の試験においては、三つの試験片についてすべて、残炎時間が１０秒以下、残じん時間が３０秒以下、炭化面積が７０ｃｍ2 以下のときを合格とし、一つの試験片についてでも、この基準に満たないときは不合格とした。但し、比較例５については、初期試験片２つを用いて試験を行い、上記と同様にして合否を判定した。
【００４１】
【表１】
【表２】
【発明の効果】
以上のように、本発明によれば、ホウ酸と尿素とリン酸とを加熱させ、反応させて得られた無機難燃剤をホウ素／ケイ素モル比が２．５〜２０の範囲となるように少量のシランカップリング剤と組み合わせることによって、耐水性ある難燃性を木材に付与することができる木材用水性難燃剤を得ることができる。しかも、このような水性難燃剤を木材に適用するに際して、刷毛塗りやスプレー塗布によることができ、既存の建築物に組み込まれた木材も容易に難燃化することができる。[0001]
BACKGROUND OF THE INVENTION
TECHNICAL FIELD The present invention relates to flame retardancy of wood, and more specifically, an aqueous flame retardant for wood capable of imparting flame retardancy with excellent water resistance to wood, a method for flame retarding wood using the same, and a product obtained by using the flame retardant. It relates to flame retardant wood.
[0002]
[Prior art]
Conventionally, a method of applying and impregnating wood with an aqueous flame retardant containing a halogen-based flame retardant, a glass-based flame retardant, a phosphorus-based flame retardant, or the like is known in order to make wood flame-retardant. However, when a halogen-based flame retardant is used, there is a problem in that wood generates harmful gas during combustion. In addition, since the water-based flame retardant is inferior in water resistance, there is a problem that the flame retardant property of the wood decreases with time because it is eluted after being applied to the wood.
[0003]
Therefore, a method of impregnating wood with a hydrolyzable metal alkoxide such as triethyl borate and hydrolyzing it into a nonflammable metal oxide in the wood (see Patent Document 1), similarly, tetraethoxy There is known a method of impregnating wood with a solution of a metal alkoxide such as silane or tetraethoxytitanium and hydrolyzing it to generate a non-combustible metal oxide in the cellular space of the wood (see Patent Document 2). ). It has also been proposed to use an aqueous flame retardant in which an alkali metal compound or an alkaline earth metal compound is combined with the metal alkoxide (see Patent Document 3). Furthermore, a flame retarding method is also known in which wood is impregnated with a special methylsiloxane oligomer containing phosphorus or boron (see Patent Documents 5 and 6).
[0004]
However, in such a flame retardant treatment using a metal alkoxide, generally, a flame retardant is injected and impregnated into wood by a method such as vacuum injection or pressure injection, so that, for example, brush coating or spraying is performed. It is difficult to apply to general existing buildings, including buildings such as cultural properties that must be applied. Furthermore, when only a metal alkoxide, especially a silane coupling agent, is applied to wood as a flame retardant, the after-flame time and the after-dust time become long, so that the flame retardant is insufficient. Moreover, since metal alkoxides are generally expensive, there is a problem that they are difficult to put into practical use.
[0005]
In order to improve the water resistance of wood flame retardant by water-based flame retardant, after applying flame retardant to wood and drying, a method of forming a coating layer made of silicone resin on the surface of the wood is also known However (see Patent Document 4), a two-stage process is required, and the process cost is still high, and there is a difficulty in practicality.
[0006]
[Patent Document 1]
JP 05-278008 A [Patent Document 2]
JP 2002-103308 A [Patent Document 3]
Japanese Patent Laid-Open No. 2001-252908 [Patent Document 4]
Japanese Patent Laid-Open No. 11-105011 [Patent Document 5]
Japanese Patent Laid-Open No. 09-038915 [Patent Document 6]
Japanese Patent Application Laid-Open No. 09-300312
[Problems to be solved by the invention]
The present invention has been made in order to solve the above-described problems in wood flame retardancy, and an aqueous flame retardant that can easily and inexpensively impart flame resistance with excellent water resistance to wood. An object of the present invention is to provide a flame-retarding method for wood to be used and flame-retardant wood obtained by using the method.
[0008]
[Means for Solving the Problems]
According to the present invention,
(A) An aqueous inorganic flame retardant comprising a reaction product obtained by heating 1 mol part of boric acid, 1 to 5 mol part of urea and 0.05 to 1 mol part of phosphoric acid to a temperature of 90 to 160 ° C. and ( B) An aqueous flame retardant for wood, comprising a silane coupling agent in a boron / silicon molar ratio of 2.5 to 20 is provided. Moreover, according to this invention, the flame retardant method of the wood characterized by apply | coating and impregnating the said water-based flame retardant for wood to a wood is provided. Furthermore, according to the present invention, there is provided flame-retardant wood obtained by treating wood with the above-mentioned wood-based water flame retardant.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The aqueous flame retardant for wood according to the present invention is:
(A) A reaction product obtained by heating 1 mol part of boric acid, 1-5 mol part of urea and 0.05-1 mol part of phosphoric acid to a temperature of 90-160 ° C, preferably 100-140 ° C. And an aqueous inorganic flame retardant comprising (B) a silane coupling agent in a boron / silicon molar ratio of 2.5 to 20.
[0010]
When reacting by heating boric acid, urea, and phosphoric acid, when less than 1 mole of urea is used relative to 1 mole of boric acid, the water solubility of the resulting reaction product decreases. This is not preferable. On the other hand, when urea is used in an amount of more than 5 parts by mole relative to 1 part by mole of boric acid, when the resulting reaction product is combined with a silane coupling agent as a flame retardant, sufficient flame retardancy is achieved with wood. Cannot be granted. Regarding phosphoric acid, when phosphoric acid is used in an amount of less than 0.05 mole part relative to 1 mole part of boric acid, the flame retardancy of the resulting reaction product is lowered, which is not preferable. On the other hand, when phosphoric acid is used in an amount of more than 1 mole part relative to 1 mole part of boric acid, the water solubility of the resulting reaction product decreases, and a flame retardant is obtained in combination with a silane coupling agent. Sometimes, sufficient flame retardancy cannot be imparted to wood.
[0011]
In order to heat and react boric acid, urea, and phosphoric acid, it is usually sufficient to heat under normal pressure for about 10 to 90 minutes. As needed, you may make it heat and react under a heating. In addition, when heating and reacting boric acid, urea, and phosphoric acid, water or a mixture of water and a small amount of a water-soluble organic solvent such as acetone, ether, methanol, ethanol, or the like may be used as a reaction solvent. Good. Accordingly, the aqueous flame retardant according to the present invention may contain a small amount of such a water-soluble organic solvent.
[0012]
According to the present invention, boric acid, urea and phosphoric acid are heated and reacted in this way, and water is added to the resulting reaction product and dissolved in water to obtain an aqueous inorganic flame retardant. . Therefore, according to the present invention, the reaction product obtained by heating and reacting boric acid, urea, and phosphoric acid is water-soluble. For example, if the aqueous solution of the aqueous inorganic flame retardant thus obtained and the silane coupling agent is mixed, the aqueous flame retardant for wood according to the present invention can be obtained.
[0013]
In the present invention, the silane coupling agent is not particularly limited, but preferably, for example, the general formula (I)
[0014]
[Chemical 1]
(In the formula, R 1 represents a reactive group or an alkyl group having a reactive group, R 2 represents an alkyl group having 1 to 4 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms. , A and b are each independently 0, 1 or 2.)
What is represented by these is used preferably.
[0016]
Examples of the reactive group R 1 include a vinyl group, and examples of the alkyl group having a reactive group include a γ-glycidoxypropyl group, a γ-acryloxypropyl group, and a γ- Examples thereof include a methacryloxypropyl group and a 2- (3,4-epoxycyclohexyl) group. Examples of the alkyl group R 2 or R 3 include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group having 3 or more carbon atoms may be linear or branched. However, preferably, the alkyl group R 2 or R 3 is a methyl group or an ethyl group.
[0017]
Accordingly, preferred silane coupling agents used in the present invention include, for example, tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and methyltripropoxysilane. , Methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltripropoxysilane, propyltributoxysilane, dimethyldiethoxysilane Alkyl alkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyl Examples include silane coupling agents having a reactive group such as dimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxypropyltriethoxysilane.
[0018]
Among them, according to the present invention, a silane coupling agent having a photoreactive group, for example, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrisilane. Ethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Triethoxysilane or the like is preferably used.
[0019]
Furthermore, according to the present invention, the flame retardant may contain a conventionally known agent. Examples of such agents include phosphite esters such as boric acid, borax, zinc borate, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, ammonium phosphate, ammonium sulfate Guanidine phosphate, alkoxides of boron and titanium, and the like. However, the medicine is not limited to those exemplified.
[0020]
The aqueous solution of the silane coupling agent preferably contains acetic acid or a pyroligneous acid solution as a dissolution aid in order to facilitate dissolution of the silane coupling agent in water.
[0021]
According to the present invention, wood can be flame-retardant by applying and impregnating wood with the above-mentioned aqueous flame retardant for wood, followed by drying. The means and method for applying and impregnating the flame retardant to the wood are not particularly limited. For example, if the object of flame retardant is a building, it is applied using a brush, spray, roll coater, etc. do it. The amount of flame retardant applied to wood is usually about 10 to 60 g / m 2 in terms of solid content, but is not limited thereto. On the other hand, when the flame retardant target is a material at a stage before being incorporated into the building, the flame retardant may be impregnated into the wood by vacuum injection or pressure injection.
[0022]
According to the present invention, it is possible to impart flame retardancy to wood by applying and impregnating the wood with an aqueous flame retardant, followed by drying. Here, in order to dry, after applying and impregnating wood with an aqueous flame retardant, it is usually necessary to leave it at room temperature for several days, but if necessary, it may be heated and dried. .
[0023]
In particular, when a photoreactive silane coupling agent as described above is used as the silane coupling agent component in the flame retardant according to the present invention, the flame retardant is applied to wood and impregnated, and then ultraviolet rays are applied. By irradiating, it is possible to prevent elution of the aqueous inorganic flame retardant and to impart flame retardancy with further excellent water resistance to wood. Thus, the reason why elution of the aqueous inorganic flame retardant can be prevented by using the photoreactive silane coupling agent as the silane coupling agent component in the flame retardant is not necessarily clear, Although the present invention is not restricted at all for such reasons, the photoreactive silane coupling agent reacts with the components in the aqueous inorganic flame retardant by light irradiation, thereby making it water-insoluble. It seems to be.
[0024]
Thus, by applying and impregnating the flame retardant according to the present invention to wood, the silane coupling agent is hydrolyzed and condensed in the wood to form a gel made of nonflammable silicon oxide, As described above, since the elution of the aqueous inorganic flame retardant is prevented, the flame retardant wood according to the present invention can be obtained by imparting water-resistant flame resistance to the wood together with the aqueous inorganic flame retardant.
[0025]
【Example】
EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
[0026]
Example 1
2 mol of boric acid, 4 mol of urea and 0.2 mol of phosphoric acid (85% by weight aqueous solution) were charged into a separable flask, heated to 110 ° C. with stirring, and reacted at this temperature for 1 hour. A powdery reaction product was obtained. Water was added to the reaction product and dissolved to obtain a water-soluble inorganic flame retardant having a solid content of 33% by weight. Separately, 50 g (0.2 mol) of γ-glycidoxypropyltrimethoxysilane was added to 50 g of 6 wt% aqueous acetic acid solution with stirring, and dissolved in an acetic acid aqueous solution to obtain an aqueous silane coupling agent solution. Then, the water-soluble inorganic flame retardant and the silane coupling agent aqueous solution were mixed to obtain an aqueous flame retardant according to the present invention having a boron / silane coupling agent silicon molar ratio of 10/1.
[0027]
This aqueous flame retardant was applied and impregnated at a dry weight of 20 g / m 2 on the surface of a cedar board (110 mm × 290 mm, thickness 15 mm, hereinafter the same), and then left at room temperature for 1 week to dry. Thus, an initial test piece for evaluating flame retardancy was obtained. Separately, this initial test piece was immersed in water (30 ° C.) for 3 hours, dried at 50 ° C. for 16 hours, and then left to room temperature to obtain a water resistance test piece for testing the water resistance of the flame retardant. .
[0028]
Example 2
In Example 1, an aqueous flame retardant according to the present invention was obtained in the same manner as in Example 1 except that a part of the 6% by weight acetic acid aqueous solution was replaced with a wood vinegar solution (1% by weight). In the same manner as in Example 1, an initial test piece and a water resistance test piece were prepared.
[0029]
Example 3
The aqueous flame retardant prepared in Example 1 was applied and impregnated at a dry weight ratio of 20 g / m 2 on the surface of the cedar board, and then irradiated with ultraviolet rays using an ultraviolet irradiation device (UVC-1212 manufactured by Ushio Electric Co., Ltd.). Irradiated for 20 seconds to obtain an initial test piece. Separately, the test piece was immersed in water (30 ° C.) for 3 hours and dried at 50 ° C. for 16 hours, and then allowed to stand at room temperature to test the water resistance of the flame retardant. It was set as the water-resistant test piece for doing.
[0030]
Example 4
In Example 1, an aqueous flame retardant according to the present invention was obtained in the same manner as in Example 1 except that γ-methacryloxypropyltrimethoxysilane was used instead of γ-glycidoxypropyltrimethoxysilane. The initial test piece and the water resistance test piece were prepared in the same manner as in Example 1.
[0031]
Example 5
In Example 1, an aqueous flame retardant was prepared in the same manner as in Example 1 except that the silicon molar ratio of the water-soluble inorganic flame retardant boron / silane coupling agent was 10/2. Were used to prepare an initial test piece and a water resistance test piece.
[0032]
Example 6
2 mol of boric acid, 8 mol of urea and 1 mol of phosphoric acid (80% by weight aqueous solution) were charged into a separable flask, heated to 110 ° C. with stirring, and reacted at this temperature for 1 hour. A powdery reaction product was obtained. Water was added to the reaction product and dissolved to obtain a water-soluble inorganic flame retardant having a solid content of 35% by weight. Separately, 50 g (0.2 mol) of γ-glycidoxypropyltrimethoxysilane was added to 50 g of 6 wt% aqueous acetic acid solution with stirring, and dissolved in an acetic acid aqueous solution to obtain an aqueous silane coupling agent solution.
[0033]
The aqueous flame retardant according to the present invention was prepared by mixing 50 parts by weight of the water-soluble inorganic flame retardant, 10 parts by weight of the silane coupling agent aqueous solution, and 50 parts by weight of the 45% by weight guanidine phosphate aqueous solution. In this aqueous flame retardant, the silicon molar ratio of the boron / silane coupling agent of the water-soluble inorganic flame retardant was 5, and the guanidine phosphate solid content was 20% by weight.
[0034]
An initial test piece and a water resistance test piece were prepared in the same manner as in Example 1 except that this aqueous flame retardant was used.
[0035]
Comparative Example 1
Without performing any flame retardant treatment on the cedar board, it was left to stand at room temperature for 1 week, dried and used as an initial test piece. Separately, this initial test piece was immersed in water (30 ° C.) for 3 hours, and 50 ° C. And dried for 16 hours, and then allowed to cool to room temperature to obtain a water resistance test piece.
[0036]
Comparative Example 2
The water-soluble inorganic flame retardant obtained in Example 1 was applied and impregnated at a dry weight ratio of 20 g / m 2 on the surface of the cedar board, then allowed to stand at room temperature for 1 week and dried, and an initial test. It was a piece. Separately, this initial test piece was immersed in water (30 ° C.) for 3 hours, dried at 50 ° C. for 16 hours, and then allowed to stand at room temperature to obtain a water resistance test piece.
[0037]
Comparative Example 3
In Example 1, an aqueous flame retardant was prepared in the same manner as in Example 1 except that the water-soluble inorganic flame retardant was mixed so that the solid content / silane coupling agent weight ratio was 10/5. Were used to prepare an initial test piece and a water resistance test piece.
[0038]
Comparative Example 4
An initial test piece and a water resistance test piece were prepared in the same manner as in Example 1 except that an aqueous guanidine phosphate solution (50% by weight) was used as a flame retardant.
[0039]
Comparative Example 5
The aqueous silane coupling agent solution prepared in Example 1 was applied and impregnated on the surface of the cedar board at a rate of 20 g / m 2 by dry weight, and then allowed to stand at room temperature for 1 week and dried to obtain an initial test piece. It was.
[0040]
The initial test piece and the water resistance test piece prepared in the above examples and comparative examples are tested for flame retardancy according to the Meckel burner method of “plywood for display” defined in the Fire Service Act enforcement regulations in accordance with the Fire Fighting Act 45 degree flammability test. did. The results are shown in Tables 1 and 2. In the test of the initial test piece, when the after flame time was 10 seconds or less, the residual dust time was 30 seconds or less, and the polycyclic area was 70 cm 2 or less, it was determined to be acceptable. In the test of the water resistance test piece, all three test pieces were accepted when the after flame time was 10 seconds or less, the residual dust time was 30 seconds or less, and the carbonization area was 70 cm 2 or less. When this standard was not met, it was rejected. However, for Comparative Example 5, a test was performed using two initial test pieces, and pass / fail was determined in the same manner as described above.
[0041]
[Table 1]
[Table 2]
【The invention's effect】
As described above, according to the present invention, an inorganic flame retardant obtained by heating and reacting boric acid, urea, and phosphoric acid has a boron / silicon molar ratio in the range of 2.5 to 20. By combining with a small amount of a silane coupling agent, it is possible to obtain an aqueous flame retardant for wood that can impart water-resistant flame resistance to wood. Moreover, when such a water-based flame retardant is applied to wood, it can be applied by brushing or spray coating, and wood incorporated in existing buildings can also be easily flame-retardant.
Claims (5)
（Ｂ）シランカップリング剤
をホウ素／ケイ素モル比２．５〜２０の範囲で含むことを特徴とする木材用水性難燃剤。(A) An inorganic flame retardant comprising a reaction product obtained by heating 1 mol part of boric acid, 1 to 5 mol part of urea and 0.05 to 1 mol part of phosphoric acid to a temperature of 90 to 160 ° C. and (B ) A water based flame retardant for wood comprising a silane coupling agent in a boron / silicon molar ratio of 2.5 to 20.
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| KR101230386B1 (en) * | 2010-05-24 | 2013-02-06 | 전일목재산업 주식회사 | Method for improving dimension stability and flame resistant of lumber |
| US11015081B2 (en) | 2018-08-22 | 2021-05-25 | Polymer Solutions Group | Fine particle size boric acid/urea dispersion, method of use in engineered wood product manufacture, method of coating wood products and product therefrom |
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