JP2019131764A - Flame-retardant composition and flame-retardant base material - Google Patents
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本発明は、難燃性組成物、それを用いる難燃性基材の製造方法およびこの方法により得られた難燃性基材に関し、更に詳細には、特定のビニルホスホン酸系モノマーと、（メタ）アクリル酸系モノマーを用いる難燃性組成物、この難燃性組成物を利用する難燃性基材の製造方法およびこの方法により得られた難燃性基材に関する。 The present invention relates to a flame retardant composition, a method for producing a flame retardant substrate using the same, and a flame retardant substrate obtained by this method, and more specifically, a specific vinylphosphonic acid monomer, The present invention relates to a flame retardant composition using a (meth) acrylic acid monomer, a method for producing a flame retardant substrate using the flame retardant composition, and a flame retardant substrate obtained by this method.
木材、紙材、樹脂、布等の基材は、一般に燃焼し易く、この燃焼に伴って有害ガスが発生することがある。そのため、公共の建築物や規模の大きい建築物の内装に使用される基材は、建築基準法から防火上の制限を受ける場合がある。また、一般住宅で使用される基材においても、安全面の問題から難燃性を求める声は増えており、今後も基材に対する難燃化のニーズは増加することが予想される。 Base materials such as wood, paper, resin, and cloth are generally easily combusted, and harmful gases may be generated with this combustion. Therefore, the base material used for the interior of a public building or a large-scale building may be subject to fire protection restrictions from the Building Standard Law. In addition, in the base materials used in ordinary houses, there is an increasing demand for flame retardancy due to safety issues, and it is expected that the need for flame retardancy for base materials will continue to increase.
一般に、基材に対して難燃性を付与する技術としては、リン化合物やハロゲン化合物、ホウ酸・ホウ砂混合物等を含んだ薬剤を基材に含浸させる方法等が知られている。特にこれらの中でも、ホウ酸・ホウ砂混合物を含んだ薬剤は、安定性が高いことから広く利用されている。 In general, as a technique for imparting flame retardancy to a substrate, a method of impregnating the substrate with a chemical containing a phosphorus compound, a halogen compound, a boric acid / borax mixture, or the like is known. Among these, drugs containing a boric acid / borax mixture are widely used because of their high stability.
例えば、ホウ酸とホウ砂を含有する水溶液に、一定の加熱および冷却処理を施して得られたホウ素化合物の水溶液を、木材や和紙等に含浸させることで、これらが高い難燃性を示すことが開示されている(特許文献１)。 For example, by impregnating wood or Japanese paper with an aqueous solution of a boron compound obtained by subjecting an aqueous solution containing boric acid and borax to a certain heating and cooling treatment, they exhibit high flame retardancy. Is disclosed (Patent Document 1).
また、ホウ素化合物と糖類とを特定の割合で混合した難燃組成物を、ポリエステル不織布やポリプロピレン不織布等に含浸させると、これらの不織布が高い難燃性を示すことが開示されている(特許文献２)。 Further, it is disclosed that when a flame retardant composition in which a boron compound and a saccharide are mixed at a specific ratio is impregnated into a polyester nonwoven fabric or a polypropylene nonwoven fabric, these nonwoven fabrics exhibit high flame retardancy (Patent Documents). 2).
しかしながら、上記技術では、基材の難燃性を高めることができるものの、多湿の環境下で使用し続けると、基材に含まれたホウ素化合物が潮解して溶出し、その結果、基材の表面にホウ素化合物が白く析出するという、いわゆる白華現象が発生し、外観が悪くなるという問題があった。 However, with the above technology, the flame retardancy of the substrate can be increased, but if it is used in a humid environment, the boron compound contained in the substrate is deliquesced and eluted, and as a result, the substrate There is a problem that a so-called white flower phenomenon occurs in which the boron compound is precipitated white on the surface and the appearance is deteriorated.
上記問題を解決する手段として、基材に難燃性を与え、且つ、白華現象を抑制するために、例えば、難燃剤、リン酸イオン、マグネシウムイオンおよびアンモニウムイオンを含有する酸性水溶液を木質材料に注入し、次に、この木質材料をアルカリ性水溶液に接触させて、木質材料の表面や内部に難溶性物質であるリン酸マグネシウムアンモニウムを生成させることにより、難燃剤の溶脱を抑制する技術が開示されている(特許文献３)。 As a means for solving the above problems, for example, an acid aqueous solution containing a flame retardant, a phosphate ion, a magnesium ion and an ammonium ion is used as a woody material in order to impart flame retardancy to the base material and to suppress the white flower phenomenon. Disclosed is a technology that suppresses the leaching of the flame retardant by bringing the wooden material into contact with an alkaline aqueous solution and generating magnesium ammonium phosphate, which is a poorly soluble substance, on the surface and inside of the wooden material. (Patent Document 3).
また、ホウ素化合物を木材に含浸させて乾燥させた後、塩化カルシウム等でホウ素化合物を不溶化させ、更に、木材の表面を防湿性の樹脂で覆う技術が開示されている(特許文献４)。 In addition, a technique is disclosed in which wood is impregnated with a boron compound and dried, and then the boron compound is insolubilized with calcium chloride or the like, and the wood surface is covered with a moisture-proof resin (Patent Document 4).
しかしながら、これらの技術は、ホウ素化合物を固定させるために、多くの薬剤を必要とし、また、製造工程が多く煩雑であり、非常に手間がかかるという問題があった。更に、木材等の難燃基材が雨水等に曝される環境下においては、白華だけではなく、水への溶出も問題となるため、高い耐水性能を付与することも求められている。 However, these techniques have a problem that a lot of chemicals are required to fix the boron compound, and the manufacturing process is complicated and very troublesome. Furthermore, in an environment where a flame-retardant base material such as wood is exposed to rainwater or the like, not only white flower but also elution into water becomes a problem, and therefore, it is required to provide high water resistance.
本発明は、上記実情を鑑みてなされたものであり、その課題は、簡単な手段によって、可燃性基材に対して難燃性、白華抑制機能、耐水性を付与することのできる難燃性組成物を提供することである。また、別の課題は、この難燃性組成物を利用する、難燃性且つ白華抑制機能、高耐水性を有する難燃性基材並びにこの難燃性基材の製造方法を提供することである。 The present invention has been made in view of the above circumstances, and its problem is that it is possible to impart flame retardancy, whitening suppression function, and water resistance to a combustible substrate by simple means. Providing a sex composition. Another object is to provide a flame retardant base material having flame retardancy and white-fade suppression function and high water resistance, and a method for producing the flame retardant base material, using this flame retardant composition. It is.
本発明者らは、上記課題を解決すべく鋭意研究を行っていたところ、ビニルホスホン酸系モノマーと、（メタ）アクリル酸系モノマーを可燃性基材に含浸させた後、これらを重合させることにより、可燃性基材の難燃性が高まり、白華が抑制されるとともに、基材の耐水性が向上することを見出し、本発明を完成した。 The inventors of the present invention have been diligently researching to solve the above-mentioned problems. After impregnating a flammable base material with a vinylphosphonic acid monomer and a (meth) acrylic acid monomer, polymerizing them. Thus, the flame retardancy of the flammable base material is increased, white bloom is suppressed, and the water resistance of the base material is improved, thereby completing the present invention.
即ち、本発明は、次の化学式（１）
で表されるビニルホスホン酸系モノマーと、次の化学式（２）
で表される（メタ）アクリル酸系モノマーとを含有することを特徴とする難燃性組成物である。
That is, the present invention has the following chemical formula (1)
And a vinylphosphonic acid monomer represented by the following chemical formula (2)
It contains the (meth) acrylic-acid type monomer represented by these, The flame retardant composition characterized by the above-mentioned.
また本発明は、可燃性基材に、前記の難燃性組成物を含浸ないし塗布し、次いで当該難燃剤組成物中のビニルホスホン酸系モノマー（１）と、（メタ）アクリル酸系モノマー（２）とを重合させることを特徴とする難燃性基材の製造方法である。 In the present invention, the flame retardant composition is impregnated or applied to a flammable substrate, and then the vinylphosphonic acid monomer (1) and the (meth) acrylic acid monomer ( 2) and a method for producing a flame retardant substrate.
更に本発明は、前記の方法により製造された難燃性基材である。 Furthermore, this invention is a flame-retardant base material manufactured by the said method.
本発明によれば、白華等の現象を抑制しながら、可燃性基材に高い難燃性と耐水性を付与することのできる難燃性組成物を提供することができる。また、本発明の製造方法によれば、特定のビニルホスホン酸系モノマーと（メタ）アクリル酸系モノマーを、可燃性基材中で重合させることで、高い難燃性と白華抑制能および耐水性能を有する難燃性基材を提供することができる。そして、この方法で得られる難燃性基材は、難燃性が高く、また、使用時において白華が抑制され、水中などでのビニルホスホン酸系モノマーと(メタ)アクリル酸系モノマーに由来する重合体の溶出を防ぐことができるため、外観に優れたものであり、例えば、建築材、家具材、内装材、構造材、装飾材、断熱材等として有利に使用できる。 ADVANTAGE OF THE INVENTION According to this invention, the flame-retardant composition which can provide high flame retardance and water resistance to a combustible base material can be provided, suppressing phenomena, such as a white flower. In addition, according to the production method of the present invention, a specific vinylphosphonic acid monomer and a (meth) acrylic acid monomer are polymerized in a flammable base material, so that high flame retardancy, whiteness suppressing ability and water resistance are achieved. A flame retardant substrate having performance can be provided. And the flame retardant substrate obtained by this method has high flame retardancy, and white blossom is suppressed at the time of use, and is derived from a vinylphosphonic acid monomer and a (meth) acrylic acid monomer in water. The polymer is excellent in appearance and can be advantageously used as, for example, a building material, furniture material, interior material, structural material, decorative material, heat insulating material, and the like.
本明細書において、難燃とは、燃えにくいことを意味し、不燃、防炎、防火、耐火の全てを含む。また、本明細書において、難燃とは、直径４０ｍｍ、高さ５５ｍｍの円柱状の木材片を７５０℃のマッフル炉の中で２０分間加熱したときの重量減少率が９９％以下であることをいい、難燃化するとは、上記重量減少率を９９％以下にすることをいう。 In this specification, a flame retardance means that it is hard to burn, and includes all of nonflammability, flameproofing, fireproofing, and fireproofing. Moreover, in this specification, a flame retardance means that the weight reduction rate when heating a 20-minute cylindrical wood piece of diameter 40mm and height 55mm in a 750 degreeC muffle furnace is 99% or less. The phrase “combustible” means that the weight reduction rate is 99% or less.
本発明の難燃性組成物（以下、「本発明組成物」という）は、次の化学式（１）
で表されるビニルホスホン酸系モノマーと、次の化学式（２）
で表される（メタ）アクリル酸系モノマーとを含有するものである。
The flame retardant composition of the present invention (hereinafter referred to as “the composition of the present invention”) has the following chemical formula (1)
And a vinylphosphonic acid monomer represented by the following chemical formula (2)
And a (meth) acrylic acid monomer represented by the formula:
本発明組成物で使用する上記式（１）で表されるビニルホスホン酸系モノマーには、式（１）中、Ｒ１が水素原子であるビニルホスホン酸と、Ｒ１が低級アルキル基であるビニルホスホン酸低級アルキルエステルが含まれる。 The vinylphosphonic acid-based monomer represented by the above formula used in the present invention the composition (1) are those wherein (1), and vinylphosphonic acid R 1 is a hydrogen atom, R 1 is a lower alkyl group Vinylphosphonic acid lower alkyl esters are included.
このうち、ビニルホスホン酸低級アルキルエステルとしては、例えば、ビニルホスホン酸ジメチル、ビニルホスホン酸ジエチル等が挙げられる。これらの中でも、ビニルホスホン酸ジメチルが好ましい。 Among these, examples of the vinylphosphonic acid lower alkyl ester include dimethyl vinylphosphonate and diethyl vinylphosphonate. Among these, dimethyl vinylphosphonate is preferable.
また、本発明組成物で使用する上記式（２）で表される（メタ）アクリル酸系モノマーとしては、例えば、アクリル酸、メタクリル酸、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル等の（メタ）アクリル酸エステルが挙げられる。これらの中でも、メタクリル酸メチルを使用することが好ましい。 Examples of the (meth) acrylic acid monomer represented by the above formula (2) used in the composition of the present invention include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, and methacrylic acid. Examples include (meth) acrylic acid esters such as ethyl. Among these, it is preferable to use methyl methacrylate.
本発明組成物中におけるビニルホスホン酸系モノマー（１）の配合量としては、１０〜３０質量％（以下、「％」で示す）、更には、１０〜２０％が好ましく、特に１０〜１５％が好ましい。また、本発明組成物の（メタ）アクリル酸系モノマー（２）の配合量としては、７０〜９０％が好ましく、８０〜９０％がより好ましい。 The compounding amount of the vinylphosphonic acid monomer (1) in the composition of the present invention is preferably 10 to 30% by mass (hereinafter referred to as “%”), more preferably 10 to 20%, particularly 10 to 15%. Is preferred. Moreover, as a compounding quantity of the (meth) acrylic-acid type monomer (2) of this invention composition, 70 to 90% is preferable and 80 to 90% is more preferable.
更に、前記ビニルホスホン酸系モノマー（１）と、前記（メタ）アクリル酸系モノマー（２）の重量比は、１：９９〜３０：７０であることが好ましい。 Furthermore, the weight ratio of the vinylphosphonic acid monomer (1) and the (meth) acrylic acid monomer (2) is preferably 1:99 to 30:70.
本発明組成物は、後記するように可燃性基材中に含浸ないしは塗布して使用するものであるため、液状ないしペースト状の形態であることが好ましい。本発明組成物で使用するモノマーは、それ自体が液状であるため、本発明組成物の調製にあたっては、特段溶媒等を使用しなくとも良いが、必要に応じて、溶媒を使用することも可能である。使用可能な溶媒の例としては、水、脂肪族炭化水素、脂環式炭化水素、アルコール、エーテル、ケトン、エステル等が挙げられる。 Since the composition of the present invention is used by impregnating or coating a combustible substrate as described later, it is preferably in a liquid or pasty form. Since the monomer used in the composition of the present invention is liquid in itself, it is not necessary to use a special solvent or the like in the preparation of the composition of the present invention, but a solvent can also be used if necessary. It is. Examples of solvents that can be used include water, aliphatic hydrocarbons, alicyclic hydrocarbons, alcohols, ethers, ketones, esters, and the like.
また、本発明においては、後記するようにビニルホスホン酸系モノマー（１）と、（メタ）アクリル酸系モノマー（２）を可燃性基材中で重合させるために重合開始剤を使用する。この重合開始剤は、上記両モノマーと同一の製剤中に配合し、可燃性基材中に同時に含浸、塗布しても良いし、両モノマーを含む製剤（第１剤）とは別の製剤（第２剤）とし、第１剤を可燃性基材に含浸、塗布した後、別に作用させても良い。（以下、本明細書中では、重合開始剤を同一製剤中に含む形態および別製剤とする形態を含め、本発明組成物という。） In the present invention, as described later, a polymerization initiator is used to polymerize the vinylphosphonic acid monomer (1) and the (meth) acrylic acid monomer (2) in the combustible substrate. This polymerization initiator may be blended in the same preparation as the above-mentioned two monomers, impregnated and applied simultaneously in a flammable base material, or a preparation different from the preparation (first agent) containing both monomers ( 2nd agent), and after impregnating and applying the 1st agent to the flammable substrate, it may be allowed to act separately. (Hereinafter, in the present specification, the composition of the present invention is included, including the form containing the polymerization initiator in the same preparation and the form of separate preparation.)
本発明組成物で使用する重合開始剤としては、ラジカル重合用の重合開始剤が好ましく、例えば、ケトンパーオキシド、ジアシルパーオキシド、ジアルキルパーオキシド、パーオキシケタール、アルキルパーオキシエステル、パーオキシカーボネート等の有機過酸化物、アゾニトリル、アゾエステル、アゾアミド等の有機アゾ化合物を挙げることができる。 The polymerization initiator used in the composition of the present invention is preferably a polymerization initiator for radical polymerization, such as ketone peroxide, diacyl peroxide, dialkyl peroxide, peroxyketal, alkyl peroxy ester, peroxy carbonate, etc. And organic azo compounds such as organic peroxides, azonitriles, azoesters, and azoamides.
本発明組成物中に重合開始剤を配合する場合の添加量は、０．１〜１０％が好ましく、０．２〜３％がより好ましい。 0.1-10% is preferable and, as for the addition amount in the case of mix | blending a polymerization initiator in this invention composition, 0.2-3% is more preferable.
本発明組成物を利用する可燃性基材の難燃化は、例えば、以下のようにして行うことができる。 The flame retardancy of the combustible substrate using the composition of the present invention can be performed, for example, as follows.
すなわち、可燃性基材に本発明組成物を含浸ないしは塗布した後、本発明組成物中のビニルホスホン酸系モノマー（１）と、（メタ）アクリル酸系モノマー（２）を可燃性基材中で重合させることにより、可燃性基材が難燃化し、難燃化基材とすることができる。 That is, after impregnating or coating the combustible base material with the composition of the present invention, the vinylphosphonic acid monomer (1) and the (meth) acrylic acid monomer (2) in the composition of the present invention are contained in the combustible base material. By polymerizing with, the flammable substrate becomes flame retardant and can be made a flame retardant substrate.
本発明組成物を利用する可燃性基材の難燃化方法（以下、「本発明方法」という）が好ましく適用される可燃性基材としては、木材、紙、織物、不織布、樹脂等の主に有機質材料で構成される基材が挙げられる。 Examples of the flammable substrate to which the flame-retardant method of flammable substrate using the composition of the present invention (hereinafter referred to as “the method of the present invention”) is preferably applied include wood, paper, woven fabric, nonwoven fabric, and resin. The base material comprised by organic material is mentioned.
このうち、木材としては、特に制限されないが、例えば、杉材、エゾマツ、ヒノキ、キリ、ベニヤ、ケヤキ、ＳＰＦ集成材（スプルス（エゾマツ）、パイン（マツ）、ファー（モミ））、竹などが挙げられる。 Of these, the wood is not particularly limited, and examples thereof include cedar, pine, cypress, drill, veneer, zelkova, SPF laminated timber (spruce, pine (pine), fur (fir)), bamboo, and the like. Can be mentioned.
また、紙としては、特に制限されないが、例えば、和紙、ふすま紙、洋紙などが、織物としても、特に制限されないが、例えば、綿布、ポリエステル織布、ポリプロピレン織布、ナイロン織布、アクリル織布、ビニロン織布、アラミド織布、ポリエチレンテレフタレート織布などが挙げられる。 Further, the paper is not particularly limited, but for example, Japanese paper, bran paper, and Western paper are not particularly limited as the woven fabric, but for example, cotton fabric, polyester woven fabric, polypropylene woven fabric, nylon woven fabric, acrylic woven fabric. , Vinylon woven fabric, aramid woven fabric, polyethylene terephthalate woven fabric, and the like.
更に、不織布としては、特に制限されないが、例えば、ポリエステル不織布、ポリプロピレン不織布、アクリル不織布、ナイロン不織布、アラミド不織布などが、樹脂としても、特に制限されないが、例えば、ポリプロピレン、ポリエチレン、ポリウレタン（硬質、軟質）、ポリスチレン、ポリ塩化ビニル、ポリカーボネート、フェノール樹脂、尿素樹脂、メラミン樹脂、酢酸ビニル樹脂、メタクリル樹脂、エポキシ樹脂、アクリル樹脂、フッ素樹脂、ＡＢＳ樹脂、ポリアセタール、変性ポリフェニレンエーテル樹脂、ポリブチレンテレフタラート樹脂、ブタジエンゴム、ネオプレンゴム、スチレンブタジエンゴム、ブタジエンアクリロニトリルゴム、イソブテンイソプレンゴムおよびこれらの複合材料の成型体およびフィルム等が挙げられる。 Further, the nonwoven fabric is not particularly limited. For example, polyester nonwoven fabric, polypropylene nonwoven fabric, acrylic nonwoven fabric, nylon nonwoven fabric, and aramid nonwoven fabric are not particularly limited as resins. For example, polypropylene, polyethylene, polyurethane (hard, soft) ), Polystyrene, polyvinyl chloride, polycarbonate, phenolic resin, urea resin, melamine resin, vinyl acetate resin, methacrylic resin, epoxy resin, acrylic resin, fluorine resin, ABS resin, polyacetal, modified polyphenylene ether resin, polybutylene terephthalate resin , Butadiene rubber, neoprene rubber, styrene butadiene rubber, butadiene acrylonitrile rubber, isobutene isoprene rubber, and moldings and films of these composite materials. .
上記可燃性基材に、本発明組成物を含浸ないし塗布する方法としては、特に制限されず、例えば、可燃性基材を本発明組成物中に浸漬する方法、本発明組成物を基材に塗布する方法等の一般的方法が挙げられる。 The method for impregnating or applying the composition of the present invention to the combustible substrate is not particularly limited. For example, the method of immersing the combustible substrate in the composition of the present invention, the composition of the present invention as a substrate. General methods such as a coating method may be mentioned.
可燃性基材を本発明組成物中に含浸する方法としては、例えば、基材を本発明組成物中に投入、浸漬し、必要に応じて、加熱および／または加圧するのが好ましい。温度や圧力の条件としては基材の種類や形状などにより適宜設定すればよく、加熱および／または加圧のために、例えば、オートクレーブ等の装置を使用することができる。 As a method for impregnating the combustible substrate into the composition of the present invention, for example, the substrate is preferably charged and immersed in the composition of the present invention, and heated and / or pressurized as necessary. The temperature and pressure conditions may be appropriately set depending on the type and shape of the substrate, and an apparatus such as an autoclave can be used for heating and / or pressurization.
また、本発明組成物を可燃性基材に塗布する方法としては、公知の塗布方法を挙げることができ、基材の種類や形状、本発明組成物および重合開始剤の粘性などにより適宜設定すれば良い。具体的には、刷毛塗り法、ブレード法、噴霧法などが例示される。また、本発明組成物が高粘度の液体である場合には、バターナイフ様のブレードを用いるのが好ましい。 In addition, examples of a method for applying the composition of the present invention to a flammable substrate include known coating methods, and may be set as appropriate depending on the type and shape of the substrate, the viscosity of the composition of the present invention and the polymerization initiator, and the like. It ’s fine. Specific examples include a brush coating method, a blade method, and a spraying method. When the composition of the present invention is a highly viscous liquid, it is preferable to use a butter knife-like blade.
なお、本発明組成物が、重合開始剤を同一製剤中に含まず、別製剤とされた形態（２剤型）である場合は、上記した含浸、塗布手段を２回行うことが好ましい。 In addition, when the composition of the present invention is in a form (two-agent type) in which the polymerization initiator is not included in the same preparation and is a separate preparation, the above-described impregnation and application means are preferably performed twice.
可燃性基材を本発明組成物で処理するに当たっては、可燃性基材の重量に対して十分過ぎるくらいの量の本発明組成物を使用することが好ましく、例えば、本発明組成物の濃度やその組成比等にもよるが、本発明組成物を含浸または塗布した後の重量増加率で５〜４００％程度、好ましくは１０〜２００％程度とすることが好ましい。重量増加率がこのような範囲内であれば、重合、乾燥工程を経ることで可燃性基材に対して十分な難燃性と白華抑制効果並びに耐水性を与えることができる。 In treating a flammable substrate with the composition of the present invention, it is preferable to use an amount of the composition of the present invention that is too large relative to the weight of the flammable substrate. Although depending on the composition ratio, etc., the weight increase rate after impregnating or applying the composition of the present invention is about 5 to 400%, preferably about 10 to 200%. If the rate of weight increase is within such a range, sufficient flame retardancy, whitening suppression effect and water resistance can be imparted to the combustible substrate through the polymerization and drying steps.
上記のように、本発明組成物を含浸ないし塗布された可燃性基材は、次に重合工程に付される。この工程は、可燃性基材中でビニルホスホン酸系モノマー（１）と、（メタ）アクリル酸系モノマー（２）を重合させるもので、ラジカル重合により行われることが好ましい。 As described above, the combustible substrate impregnated or coated with the composition of the present invention is then subjected to a polymerization step. This step polymerizes the vinylphosphonic acid monomer (1) and the (meth) acrylic acid monomer (2) in the combustible substrate, and is preferably performed by radical polymerization.
この重合工程は、前記した重合開始剤の存在下、加熱することにより行われる。この加熱の温度は、重合開始剤の種類に応じて適宜選択すれば良いが、重合開始剤の１０時間半減期温度以上が好ましい。 This polymerization step is performed by heating in the presence of the polymerization initiator described above. The heating temperature may be appropriately selected according to the type of the polymerization initiator, but is preferably 10 hours half-life temperature or higher of the polymerization initiator.
上記の重合工程が終了した後の可燃性基材は、そのままで難燃性基材として使用することもできるが、基材中で残存するモノマーの重合促進や、また、本発明組成物から持ち込まれた成分、例えば溶媒としての水の除去を目的で加熱処理を行うことが好ましい。 The combustible base material after the completion of the above polymerization step can be used as a flame retardant base material as it is, but the polymerization of monomers remaining in the base material is promoted or brought from the composition of the present invention. It is preferable to perform a heat treatment for the purpose of removing the components, for example water as a solvent.
この加熱処理の方法およびその条件としては、特に制限されず、基材が変質、変形しない範囲で適宜設定すればよいが、残存モノマーの重合反応が進行し、溶媒などの水分が除去される条件、例えば、８０〜１２５℃で、２４〜４８時間乾燥するのが好ましい。また、乾燥には、定温乾燥器ＥＯＰ−４５０Ｂ（アズワン社製）等の装置を用いることもできる。 The heat treatment method and its conditions are not particularly limited and may be appropriately set within a range in which the base material is not altered or deformed. Conditions under which the polymerization reaction of the residual monomer proceeds and moisture such as a solvent is removed. For example, it is preferable to dry at 80 to 125 ° C. for 24 to 48 hours. In addition, a device such as a constant temperature dryer EOP-450B (manufactured by ASONE) can be used for drying.
上記加熱乾燥した後の難燃性基材は、基材の材質や形状などにもよるが、難燃処理前の可燃性基材と比べ、その重量増加率が１０〜３００％程度であることが好ましく、５０〜１００％がより好ましい。乾燥後の重量増加率がこのような範囲内であれば、基材に対して十分な難燃性と白華抑制効果並びに耐水性を与えることができる。 Although the flame-retardant base material after the above-mentioned heat drying depends on the material and shape of the base material, the weight increase rate is about 10 to 300% compared to the flammable base material before the flame-retardant treatment. Is preferable, and 50 to 100% is more preferable. If the rate of weight increase after drying is within such a range, sufficient flame retardancy, whiteness suppression effect and water resistance can be imparted to the substrate.
以上のようにして得られた本発明難燃性基材は、可燃性基材中でビニルホスホン酸系モノマー（１）と、（メタ）アクリル酸系モノマー（２）が重合、高分子化し、リン化合物を基材構造中に固定したものであるため、難燃性が高く、白華抑制機能を持ち且つ耐水性に優れたものである。 The flame retardant substrate of the present invention obtained as described above is a polymerized and polymerized vinyl phosphonic acid monomer (1) and (meth) acrylic acid monomer (2) in a flammable substrate, Since the phosphorus compound is fixed in the base material structure, it has high flame retardancy, has a function of suppressing whiteness, and is excellent in water resistance.
次に、実施例、参考例および製剤例を挙げ、本発明を更に詳細に説明するが、本発明はこれら実施例等に何ら制約されるものではない。 Next, although an Example, a reference example, and a formulation example are given and this invention is demonstrated further in detail, this invention is not restrict | limited at all by these Examples.
実 施 例 １
＜難燃性組成物の作製＞
ビニルホスホン酸ジメチル（丸善石油化学社製）を１３部、メタクリル酸メチル（和光純薬工業社製）を８５部、重合開始剤として２，２’−アゾビス（イソ酪酸）ジメチルを２部それぞれ混合し、濁りの無い清澄な溶液として難燃性組成物Ａを得た。
Example 1
<Production of flame retardant composition>
13 parts of dimethyl vinylphosphonate (manufactured by Maruzen Petrochemical Co., Ltd.), 85 parts of methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2 parts of 2,2′-azobis (isobutyric acid) dimethyl as a polymerization initiator are mixed. The flame retardant composition A was obtained as a clear solution without turbidity.
＜難燃性基材の作製＞
上記難燃性組成物Ａ ５００ｍＬ中に、４０ｍｍ×４０ｍｍ×４０ｍｍに裁断した杉材（絶乾比重０．２６〜０．３１）をそれぞれ投入し、オートクレーブにより、１ＭＰａ、３０℃で、２４時間加圧処理を行った。その後、１１５℃で２４時間乾燥処理を行うことで難燃性基材（本発明難燃性基材）を得た。
<Production of flame retardant substrate>
Cedarwood (absolute specific gravity 0.26 to 0.31) cut into 40 mm × 40 mm × 40 mm is put into 500 mL of the flame retardant composition A, and the mixture is heated at 1 MPa and 30 ° C. for 24 hours by an autoclave. Pressure treatment was performed. Then, the flame-retardant base material (this invention flame-retardant base material) was obtained by performing a drying process at 115 degreeC for 24 hours.
比 較 例 １
＜難燃性組成物の作製＞
イオン交換水３５部中にホウ酸２９部、ホウ砂３６部をそれぞれ混合し、濁りの無い清澄な溶液として難燃性組成物Ｂを得た。
Comparative Example 1
<Production of flame retardant composition>
29 parts of boric acid and 36 parts of borax were mixed in 35 parts of ion-exchanged water to obtain a flame retardant composition B as a clear solution without turbidity.
＜難燃性基材の作製＞
上記難燃性組成物Ｂ １６００ｍＬ中に、４０ｍｍ×４０ｍｍ×４０ｍｍに裁断した杉材（絶乾比重０．２６〜０．３１）をそれぞれ投入し、オートクレーブにより、１ＭＰａ、８０℃で、２４時間加圧処理を行った。
<Production of flame retardant substrate>
Cedar timber (absolute specific gravity 0.26 to 0.31) cut into 40 mm × 40 mm × 40 mm is put into 1600 mL of the flame retardant composition B, and the mixture is heated at 1 MPa and 80 ° C. for 24 hours by an autoclave. Pressure treatment was performed.
その後、１１５℃で２４時間乾燥処理を行った。得られた基材を上記難燃性組成物Ａ ５００ｍＬ中に投入し、オートクレーブにより、１ＭＰａ、３０℃で、２４時間加圧処理を行った。その後、１１５℃で２４時間乾燥処理を行うことで難燃性基材（難燃性基材Ｂ）を得た。 Then, the drying process was performed at 115 degreeC for 24 hours. The obtained base material was put into 500 mL of the flame retardant composition A, and subjected to pressure treatment at 1 MPa and 30 ° C. for 24 hours by an autoclave. Then, the flame-retardant base material (flame-retardant base material B) was obtained by performing a drying process at 115 degreeC for 24 hours.
実 施 例 ２
上記実施例１および比較例１で得た難燃性基材について、各組成物の含浸前の杉材の重量と、含浸乾燥後の杉材の重量の差から、重量増加率を求めた。また、得られた難燃性基材について、以下の方法で燃焼試験、白華試験、耐水試験を行った。これら結果を組成とともに表１に示す。
Example 2
About the flame-retardant base material obtained in the said Example 1 and the comparative example 1, the weight increase rate was calculated | required from the difference of the weight of the cedar material before the impregnation of each composition, and the weight of the cedar material after the impregnation drying. Moreover, about the obtained flame-retardant base material, the combustion test, the white flower test, and the water resistance test were done with the following method. These results are shown in Table 1 together with the composition.
＜燃焼試験＞
各難燃性基材（杉材）を７５０℃に保持したマッフル炉で２０分間加熱し、その際の重量減少率から難燃性を評価した。
<Combustion test>
Each flame-retardant base material (cedar material) was heated for 20 minutes in a muffle furnace maintained at 750 ° C., and the flame retardance was evaluated from the weight reduction rate at that time.
＜白華試験＞
白華現象の評価は、目視により基材の表面に現れた白華の有無を確認して行った。
<White flower test>
The white flower phenomenon was evaluated by confirming the presence or absence of white flower that appeared on the surface of the substrate.
＜耐水試験＞
上記、難燃性基材を２０倍容のイオン交換水中に７日間浸漬させた後、試験片を取り出し、重量減少率から耐水性を評価した。
<Water resistance test>
After the flame retardant substrate was immersed in 20 times volume of ion exchange water for 7 days, the test piece was taken out and water resistance was evaluated from the weight reduction rate.
この結果、ビニルホスホン酸系モノマーと（メタ）アクリル酸系モノマーを配合した実施例１の難燃性組成物で処理した杉材は難燃性を示しつつも白華が発生しないことが確認された。更に、耐水試験後の重量減少率も低いことから難燃性組成物の溶出を防ぎ、湿潤環境下においても性能低下を起こさないことが確認された。 As a result, it was confirmed that the cedar wood treated with the flame retardant composition of Example 1 blended with the vinylphosphonic acid monomer and the (meth) acrylic acid monomer showed flame retardancy but did not generate white flower. It was. Furthermore, since the rate of weight reduction after the water resistance test is low, it was confirmed that the flame-retardant composition was prevented from being eluted and the performance was not deteriorated even in a wet environment.
一方、一般的に使用される難燃性組成物であるホウ酸・ホウ砂を加えた難燃性組成物で予め処理した比較例１は、難燃性を示すものの、白華が発生した。更には耐水試験後の重量減少率も高いことから、難燃性組成物が溶出し、安定性に欠けることが確認された。 On the other hand, although the comparative example 1 previously processed with the flame retardant composition which added the boric acid and borax which are generally used flame retardant compositions shows flame retardancy, the white flower generate | occur | produced. Furthermore, since the rate of weight reduction after the water resistance test was also high, it was confirmed that the flame retardant composition was eluted and lacked stability.
製 剤 例 １
２剤型難燃剤
＜ 組 成 ＞
Ａ剤：
ビニルホスホン酸 ２０％
アクリル酸 ８０％
Ｂ剤：
ＡＩＢＮ （重合開始剤） １％
エタノール （溶剤） ９９％
Product example 1
Two-component flame retardant <Composition>
Agent A:
20% vinylphosphonic acid
Acrylic acid 80%
Agent B:
AIBN (polymerization initiator) 1%
Ethanol (solvent) 99%
＜ 使用法 ＞
まず可燃性基材をＡ剤に十分浸漬し、次いで加圧加熱する。次いで、これをＢ剤に浸漬後、加熱し、重合、乾燥する。
<Usage>
First, the flammable substrate is sufficiently immersed in the agent A, and then heated under pressure. Next, this is immersed in the agent B, heated, polymerized and dried.
製 剤 例 ２
塗布型難燃剤
＜ 組 成 ＞
ビニルホスホン酸 ２０％
アクリル酸 ７９％
ＡＩＢＮ （重合開始剤） １％
Product example 2
Application type flame retardant <Composition>
20% vinylphosphonic acid
Acrylic acid 79%
AIBN (polymerization initiator) 1%
＜ 使用法 ＞
可燃性基材上に、刷毛を用いて上記難燃剤の十分量を塗布する。組成物が基材中に浸透した後、基材を加熱し、重合、乾燥する。
<Usage>
A sufficient amount of the flame retardant is applied onto the flammable substrate using a brush. After the composition has penetrated into the substrate, the substrate is heated, polymerized and dried.
本発明によれば、難燃性が高く、白華を抑制することができ、且つ、配合成分が溶出することの無い難燃性組成物を提供することができる。また、この難燃性組成物で可燃性基材を処理することで、難燃性が高く、また、使用時において白華が抑制され、更に外観に優れた難燃性基材に変えることができる。更にこの難燃性基材は湿潤環境下においても性能低下することがないため、難燃剤分野等において、極めて有用である。 According to the present invention, it is possible to provide a flame retardant composition that has high flame retardancy, can suppress white flower, and does not cause the blended components to elute. In addition, by treating a flammable substrate with this flame retardant composition, the flame retardant is high, and in use, white bloom is suppressed, and it can be changed to a flame retardant substrate having an excellent appearance. it can. Furthermore, since this flame retardant substrate does not deteriorate in performance even in a humid environment, it is extremely useful in the field of flame retardants.
Claims (9)
で表されるビニルホスホン酸系モノマーと、次の化学式（２）
で表される（メタ）アクリル酸系モノマーとを含有することを特徴とする難燃性組成物。 The following chemical formula (1)
And a vinylphosphonic acid monomer represented by the following chemical formula (2)
A flame retardant composition comprising a (meth) acrylic acid monomer represented by:
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