JP4188500B2 - Nitrogen-containing organophosphorus compound and flame retardant resin composition - Google Patents

Description

ここで、ｍは１または２であり、Ｒ^１、Ｒ^２およびＲ^３は、それぞれ独立に、Ｃ１〜Ｃ１０のアルキル基、アルケニル基もしくはシクロアルキル基、または、
【化４】

（Ｒ^７はＣ１〜Ｃ１０のアルキル基、ｎは０〜３の整数である。）で表されるアリール基であり、Ｒ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水素またはＣ１〜Ｃ１０のアルキル基、アルケニル基もしくはシクロアルキル基である。
【００１１】
また、本発明の難燃性樹脂組成物は、樹脂と、上記一般式（１）で示される含窒素有機リン化合物を含有するものである。
【００１２】
【発明の実施の形態】
本発明の含窒素有機リン化合物は、例として、ハロリン酸ジエステルとグアナミン類の脱ハロゲン化水素反応により得られる。
【００１３】
ここで、一方の原料であるハロリン酸ジエステルは、下記一般式（２）で表される。
【００１４】
【化５】

式中、Ｒ^１およびＲ^２は上記一般式（１）と同じであり、Ｘはハロゲン原子、例えば塩素又は臭素である。
【００１５】
より具体的には、クロロリン酸ジフェニル、クロロリン酸ジキシリル、クロロリン酸ジクレジル、ブロモリン酸ジフェニルが好適な例として挙げられる。
【００１６】
他方の原料であるグアナミン類は、下記一般式（３）で表される。
【００１７】
【化６】

式中、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は上記一般式（１）と同じである。
【００１８】
より具体的には、ベンゾグアナミン、アセトグアナミンが好適な例として挙げられる。
【００１９】
上記ハロリン酸ジエステルとグアナミン類の脱ハロゲン化水素反応は、通常、脱ハロゲン化水素剤を用いて、無水条件下、８０〜２００℃の温度で、２〜１０時間行う。但し、脱ハロゲン化水素剤は使用しなくても良い。
【００２０】
ここで、脱ハロゲン化水素剤としては、トリエチルアミン、ピリジン等の第３級アミンを好適な例として挙げることができる。この場合、使用するアミンの量は、ハロリン酸ジエステルの等モル〜２倍モルが望ましい。
【００２１】
本発明の含窒素有機リン化合物はあらゆる樹脂に対して使用することができる。すなわち、本発明の難燃性樹脂組成物において、前記含窒素有機リン化合物と配合する樹脂は、特に限定されない。例えば、ポリオレフィン、ポリスチレン、ＡＢＳ樹脂、ポリエステル、ポリカーボネート、ポリアミド、ポリフェニレンオキサイド等の熱可塑性樹脂だけでなく、エポキシ樹脂、フェノール樹脂、ウレタン樹脂等の熱硬化性樹脂にも使用可能である。
【００２２】
該含窒素有機リン化合物の樹脂への配合量は、使用する樹脂や必要とされる難燃性能によって異なるが、通常、樹脂１００重量部に対して１〜１００重量部である。
【００２３】
また、該含窒素有機リン化合物の樹脂への配合方法は、特に限定されない。熱硬化性樹脂に配合する場合、例えば、予め樹脂と含窒素有機リン化合物を十分に混合した後、硬化させることができる。また、熱可塑性樹脂に配合する場合、例えば、二軸押出機等で樹脂に含窒素有機リン化合物を混練した後、射出成形機等で成形することができる。
【００２４】
なお、本発明の難燃性樹脂組成物においては、他の難燃剤を併用したり、他の配合剤、例えばタルク、マイカのような無機充填剤、ガラス繊維や炭素繊維のような補強剤、紫外線吸収剤、光安定剤、酸化防止剤、熱安定剤、帯電防止剤、顔料、離型剤、相溶化剤、耐衝撃改良剤等を添加してもよい。
【００２５】
【実施例】
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。
【００２６】
実施例１
撹拌機、滴下ロート、冷却器および温度計を備えた５００ｍｌの三つ口フラスコに、クロロリン酸ジフェニル５３．７ｇ（０．２ｍｏｌ）、ベンゾグアナミン１８．７ｇ（０．１ｍｏｌ）、トリエチルアミン２２．３ｇ（０．２２ｍｏｌ）、ジオキサン１５０ｍｌを仕込み、１００℃で３時間反応した。この反応物に塩化メチレン３００ｍｌを加えて希釈し、希塩酸で洗浄した後、水洗した。その後、塩化メチレンを留去し、メタノール５００ｍｌ中に加えて結晶を析出させ、ろ過、乾燥して、生成物（Ａ）４１．３ｇを得た。
【００２７】
この生成物（Ａ）のＩＲスペクトルを測定したところ、ν＝１２５５ｃｍ^−１にＰ＝Ｏ伸縮振動のピーク、ν＝９６３ｃｍ^−１にＰ−Ｎ伸縮振動およびＰ−Ｏ伸縮振動のピークがあった。また、ＤＴＡ（示差熱分析）を測定したところ、１６２．８℃と１８１．２℃に融点と思われるピークが観測された。また、１％減量温度は３１６℃、５％減量温度は３３５℃であった。
【００２８】
この生成物（Ａ）について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定すると２つのピークが現れ、これらはＵＶ（２５４ｎｍ）検出器で測定したピーク面積比で６１対３９であつた。
【００２９】
それぞれを分取し、質量分析したところ、生成物（Ａ）は、下記式（Ａ１）で表されるベンゾグアナミンのモノリン酸アミド（分子量：４２０）３９重量％と、下記式（Ａ２）で表されるベンゾグアナミンのジリン酸アミド（分子量：６５２）６１重量％とからなることが分かった。
【００３０】
【化７】

実施例２
撹拌機、滴下ロート、冷却器および温度計を備えた５００ｍｌの三つ口フラスコに、クロロリン酸ジキシリル８２．１ｇ（０．２２ｍｏｌ）、ベンゾグアナミン１８．７ｇ（０．１ｍｏｌ）、トリエチルアミン２４．３ｇ（０．２４ｍｏｌ）、ジオキサン１５０ｍｌを仕込み、１００℃で６時間反応した。この反応物に水１５０ｍｌを加えて希釈し、塩酸でｐＨ＝１に調整した後、メタノール５００ｍｌ中に加えて結晶を析出させ、ろ過、乾燥して、生成物（Ｂ）５１．０ｇを得た。
【００３１】
この生成物（Ｂ）のＩＲスペクトルを測定したところ、ν＝１２４８ｃｍ^−１，１２６７ｃｍ^−１にＰ＝Ｏ伸縮振動のピーク、ν＝９３９ｃｍ^−１，９６９ｃｍ^−１にＰ−Ｎ伸縮振動およびＰ−Ｏ伸縮振動のピークがあった。また、ＤＴＡ（示差熱分析）を測定したところ、２７１．０℃と２７４．７℃に融点と思われるピークが観測された。また、１％減量温度は３３０℃、５％減量温度は３４６℃であった。
【００３２】
この生成物（Ｂ）について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定すると２つのピークが現れ、これらはＵＶ（２５４ｎｍ）検出器で測定したピーク面積比で１５対８５であった。
【００３３】
それぞれを分取し、質量分析したところ、生成物（Ｂ）は、下記式（Ｂ１）で表されるベンゾグアナミンのモノリン酸アミド（分子量：４７６）８５重量％と、下記式（Ｂ２）で表されるベンゾグアナミンのジリン酸アミド（分子量：７６４）１５重量％とからなることが分かった。
【００３４】
【化８】

実施例３
撹拌機、滴下ロート、冷却器および温度計を備えた５００ｍｌの三つ口フラスコに、クロロリン酸ジキシリル８９．６ｇ（０．２４ｍｏｌ）、アセトグアナミン１５．０ｇ（０．１２ｍｏｌ）、トリエチルアミン５０．６ｇ（０．５０ｍｏｌ）、ジオキサン１５０ｍｌを仕込み、１００℃で６時間反応した。この反応物に塩化メチレン１５０ｍｌを加えて希釈し、塩酸で洗浄した後、塩化メチレンを留去し、イソプロパノール５００ｍｌ中に加えて結晶を析出させた。ろ過後、イソプロパノールで再結晶したものを、ろ過、乾燥して、生成物（Ｃ）５３．４ｇを得た。
【００３５】
この生成物（Ｃ）のＩＲスペクトルを測定したところ、ν＝１２４８ｃｍ^−１，１２６７ｃｍ^−１にＰ＝Ｏ伸縮振動のピーク、ν＝９３６ｃｍ^−１，９６７ｃｍ^−１にＰ−Ｎ伸縮振動およびＰ−Ｏ伸縮振動のピークがあった。また、ＤＴＡ（示差熱分析）を測定したところ、２０７．５℃と２４１．６℃に融点と思われるピークが観測された。また、１％減量温度は２０９℃、５％減量温度は２９６℃であった。
【００３６】
この生成物（Ｃ）について、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）測定すると２つのピークが現れ、これらはＵＶ（２５４ｎｍ）検出器で測定したピーク面積比で２６対７４であった。
【００３７】
それぞれを分取し、質量分析したところ、生成物（Ｃ）は、下記式（Ｃ１）で表されるアセトグアナミンのモノリン酸アミド（分子量：３５７）７４重量％と、下記式（Ｃ２）で表されるアセトグアナミンのジリン酸アミド（分子量：５８９）２６重量％とからなることが分かった。
【００３８】
【化９】

実施例４〜６および比較例１
樹脂としてビスフェノールＡ型エポキシ樹脂（商品名：エピコート８２８、油化シェルエポキシ社製）８９重量部、硬化剤としてジエチレントリアミン１１重量部を用いて、難燃剤１５重量部と混合した。難燃剤としては、実施例４では上記実施例１の生成物（Ａ）を、実施例５では上記実施例２の生成物（Ｂ）を、実施例６では上記実施例３の生成物（Ｃ）を、比較例１ではポリリン酸アンモニウム（商品名：スミセーフ−Ｐ、住友化学工業(株)製）を、それぞれ用いた。
【００３９】
得られた混合物は、脱気後、６０℃で３０分間加熱し、その後、１００℃で１５分間、熱プレスを行って、平板を作成した。得られた平板を切り出して、所定の形状の試験片を作成し、難燃性試験および耐水性試験を行った。結果を表１に示す。
【００４０】
【表１】

各測定方法は以下の通りである。
【００４１】
難燃性試験：酸素指数の測定をＪＩＳ−Ｋ−７２０１に準拠して行った。また、ＵＬ９４に準拠した垂直燃焼試験（Ｖ−０〜Ｖ−２）を行った（厚み１／８インチの試験片）。
【００４２】
耐水性試験：２．５ｃｍ×２．５ｃｍ（厚さ１／８インチ）の試験片を８０℃の温水中に２日間浸漬したときの難燃剤の溶出率を調べた。
【００４３】
実施例７〜９および比較例２，３
樹脂としてポリプロピレン（商品名：チッソポリプロＫ１０１４、チッソ社製）１００重量部を用いて、難燃剤２０重量部を配合し、２００℃で熱ロールにより混練した。難燃剤としては、実施例７では上記実施例１の生成物（Ａ）を、実施例８では上記実施例２の生成物（Ｂ）を、実施例９では上記実施例３の生成物（Ｃ）を、比較例２ではポリリン酸アンモニウム（商品名：スミセーフ−Ｐ、住友化学工業(株)製）を、比較例３では下記式（Ｄ）で表されるメラミン誘導体の含窒素有機リン化合物を、それぞれ用いた。
【００４４】
【化１０】

得られた混練物を２００℃、１５０ｋｇ／ｃｍ^２で３分間熱プレスして、所定の形状の試験片を作成し、難燃性試験、引張試験、耐水性試験および耐熱性試験を行った。結果を表２に示す。
【００４５】
【表２】

ここで、引張試験と耐熱性試験の測定方法は以下の通りである。
【００４６】
引張試験：ＪＩＳ−Ｋ−７１１３に準拠して、２号試験片を用いて行った。
【００４７】
耐熱性試験：射出成型機に２００℃で４０分間滞留させた後、色調変化を色差計で測定した。
【００４８】
【発明の効果】
上記実施例にも見られるように、本発明の含窒素有機リン化合物を熱可塑性樹脂もしくは熱硬化性樹脂に添加して使用した場合には、難燃性、耐水性、熱安定性に優れ、しかも物性低下の小さい難燃性樹脂が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a nitrogen-containing organophosphorus compound that is mainly useful as a flame retardant for resins, and a flame retardant resin composition containing the compound.
[0002]
[Prior art]
Conventionally, various substances have been used as resin flame retardants, and in recent years, flame retardants containing no halogen have attracted attention for safety reasons.
[0003]
For example, as a flame retardant for a thermoplastic resin, a flame retardant containing no halogen in an alloy of ABS resin (acrylonitrile-butadiene-styrene copolymer) and polycarbonate, or an alloy of impact-resistant polystyrene and polyphenylene oxide. It is known to add a phosphate ester compound, melamine cyanurate or the like in order to obtain a functional resin. Similarly, many methods using phosphate ester compounds, melamine derivatives, and triazine derivatives have been reported for the flame retardants of phenol-based and epoxy-based thermosetting resins.
[0004]
In addition, it is a well-known fact that a phosphorus element and a nitrogen element exhibit a synergistic effect as a flame retardant. For example, ammonium phosphate or aromatic phosphate is used in combination as a phosphorus source, and melamine is used in combination as a nitrogen source. Yes.
[0005]
[Problems to be solved by the invention]
However, these flame retardants have a problem of low water resistance and thermal stability. In addition, a large amount of flame retardant is required to obtain the desired flame retardancy when added to the resin, and as a result, the resin due to poor dispersion due to poor moldability or poor compatibility There is a problem that the physical properties are lowered.
[0006]
Japanese Patent Application Laid-Open No. 8-12692 proposes a nitrogen-containing organophosphorus compound having a high phosphorus and nitrogen content, water resistance and good thermal stability for such a flame retardant. However, this nitrogen-containing organophosphorus compound is an organophosphorus compound of a melamine derivative obtained by dehydrohalogenating a haloamine diester with a halophosphate diester. As is clear from the comparative examples described later, Due to the poor compatibility, there is a problem that the physical properties of the resin are lowered due to poor dispersion and the water resistance is not sufficient.
[0007]
The present invention has been made in view of the above problems, and is a nitrogen-containing organophosphorus compound that is excellent in flame retardancy, water resistance and thermal stability, and has a small decrease in resin physical properties when added to a resin, and It aims at providing the resin composition excellent in the flame retardance which mix | blended this compound.
[0008]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that when a nitrogen-containing organophosphorus compound that is a specific guanamine derivative having at least one phosphoramide group in the molecule is added to a resin In addition, the present inventors have found that the flame retardancy, water resistance and thermal stability are excellent, and that the deterioration of the resin physical properties is small, and the present invention has been completed.
[0009]
The nitrogen-containing organophosphorus compound of the present invention is represented by the following general formula (1).
[0010]
[Chemical 3]

Here, m is 1 or 2, and R ¹ , R ² and R ³ are each independently a C1-C10 alkyl group, alkenyl group or cycloalkyl group, or
[Formula 4]

Wherein R ⁷ is a C1 to C10 alkyl group and n is an integer of 0 to 3, and R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen or C1 to C10. An alkyl group, an alkenyl group or a cycloalkyl group.
[0011]
Moreover, the flame-retardant resin composition of this invention contains resin and the nitrogen-containing organophosphorus compound shown by the said General formula (1).
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The nitrogen-containing organophosphorus compound of the present invention is obtained, for example, by a dehydrohalogenation reaction between a halophosphoric acid diester and a guanamine.
[0013]
Here, the halophosphoric diester which is one raw material is represented by the following general formula (2).
[0014]
[Chemical formula 5]

In the formula, R ¹ and R ² are the same as those in the general formula (1), and X is a halogen atom such as chlorine or bromine.
[0015]
More specifically, preferred examples include diphenyl chlorophosphate, dixyl chlorophosphate, dicresyl chlorophosphate, and diphenyl bromophosphate.
[0016]
The other raw material, guanamines, is represented by the following general formula (3).
[0017]
[Chemical 6]

In the formula, R ³ , R ⁴ , R ⁵ and R ⁶ are the same as those in the general formula (1).
[0018]
More specifically, preferred examples include benzoguanamine and acetoguanamine.
[0019]
The dehydrohalogenation reaction of the halophosphate diester and guanamine is usually performed using a dehydrohalogenating agent at a temperature of 80 to 200 ° C. for 2 to 10 hours under anhydrous conditions. However, a dehydrohalogenating agent need not be used.
[0020]
Here, as a dehydrohalogenating agent, tertiary amines, such as a triethylamine and a pyridine, can be mentioned as a suitable example. In this case, the amount of amine to be used is preferably equimolar to double molar of the halophosphoric acid diester.
[0021]
The nitrogen-containing organophosphorus compound of the present invention can be used for any resin. That is, in the flame retardant resin composition of the present invention, the resin blended with the nitrogen-containing organic phosphorus compound is not particularly limited. For example, it can be used not only for thermoplastic resins such as polyolefin, polystyrene, ABS resin, polyester, polycarbonate, polyamide and polyphenylene oxide, but also for thermosetting resins such as epoxy resin, phenol resin and urethane resin.
[0022]
The amount of the nitrogen-containing organophosphorus compound added to the resin varies depending on the resin used and the required flame retardancy, but is usually 1 to 100 parts by weight with respect to 100 parts by weight of the resin.
[0023]
Moreover, the compounding method of this nitrogen-containing organophosphorus compound to resin is not specifically limited. When blended with a thermosetting resin, for example, the resin and the nitrogen-containing organophosphorus compound can be sufficiently mixed and then cured. Moreover, when mix | blending with a thermoplastic resin, after knead | mixing a nitrogen-containing organophosphorus compound with resin with a twin-screw extruder etc., it can shape | mold with an injection molding machine etc., for example.
[0024]
In the flame-retardant resin composition of the present invention, other flame retardants are used in combination, other compounding agents, for example, inorganic fillers such as talc and mica, reinforcing agents such as glass fibers and carbon fibers, Ultraviolet absorbers, light stabilizers, antioxidants, heat stabilizers, antistatic agents, pigments, mold release agents, compatibilizers, impact resistance improvers, and the like may be added.
[0025]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples.
[0026]
Example 1
A 500 ml three-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer was charged with 53.7 g (0.2 mol) of diphenyl chlorophosphate, 18.7 g (0.1 mol) of benzoguanamine, and 22.3 g (0 of triethylamine). .22 mol) and 150 ml of dioxane were charged and reacted at 100 ° C. for 3 hours. The reaction product was diluted with 300 ml of methylene chloride, washed with dilute hydrochloric acid, and then washed with water. Thereafter, methylene chloride was distilled off, and the residue was added to 500 ml of methanol to precipitate crystals, filtered and dried to obtain 41.3 g of product (A).
[0027]
As a result of measuring an IR spectrum of the product (A), P to ν = 1255cm ^-1 = O stretching vibration peak, there was a peak of P-N stretching vibration and P-O stretching vibration ν = 963cm ^-1 . Moreover, when DTA (differential thermal analysis) was measured, peaks considered to be melting points were observed at 162.8 ° C. and 181.2 ° C. The 1% weight loss temperature was 316 ° C, and the 5% weight loss temperature was 335 ° C.
[0028]
For this product (A), two peaks appeared when measured by gel permeation chromatography (GPC), and the peak area ratio measured by a UV (254 nm) detector was 61:39.
[0029]
When each was fractionated and subjected to mass spectrometry, the product (A) was represented by 39% by weight of benzoguanamine monophosphate amide (molecular weight: 420) represented by the following formula (A1) and the following formula (A2). Benzoguanamine diphosphoric acid amide (molecular weight: 652) 61% by weight.
[0030]
[Chemical 7]

Example 2
In a 500 ml three-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 82.1 g (0.22 mol) of dixylchlorophosphate, 18.7 g (0.1 mol) of benzoguanamine, 24.3 g of triethylamine (0 .24 mol) and 150 ml of dioxane were charged and reacted at 100 ° C. for 6 hours. The reaction product was diluted by adding 150 ml of water, adjusted to pH = 1 with hydrochloric acid, then added to 500 ml of methanol to precipitate crystals, filtered and dried to obtain 51.0 g of product (B). .
[0031]
As a result of measuring an IR spectrum of the product ^{(B), ν = 1248cm -1} , a peak of P = O stretching vibration ^{1267cm -1, ν = 939cm -1,} P-N stretching vibration and 969cm ^-1 P- There was a peak of O stretching vibration. Moreover, when DTA (differential thermal analysis) was measured, peaks considered to be melting points were observed at 271.0 ° C. and 274.7 ° C. The 1% weight loss temperature was 330 ° C, and the 5% weight loss temperature was 346 ° C.
[0032]
About this product (B), when the gel permeation chromatography (GPC) measurement, two peaks appeared, and these were 15:85 in the peak area ratio measured with the UV (254 nm) detector.
[0033]
When each was fractionated and subjected to mass spectrometry analysis, the product (B) was represented by 85 wt% of benzoguanamine monophosphate amide (molecular weight: 476) represented by the following formula (B1) and the following formula (B2). Benzoguanamine diphosphoric acid amide (molecular weight: 764) and 15% by weight.
[0034]
[Chemical 8]

Example 3
In a 500 ml three-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 89.6 g (0.24 mol) of dixyl chlorophosphate, 15.0 g (0.12 mol) of acetoguanamine, 50.6 g of triethylamine ( 0.50 mol) and 150 ml of dioxane were charged and reacted at 100 ° C. for 6 hours. The reaction product was diluted with 150 ml of methylene chloride, washed with hydrochloric acid, and then the methylene chloride was distilled off and added to 500 ml of isopropanol to precipitate crystals. After filtration, the product recrystallized with isopropanol was filtered and dried to obtain 53.4 g of product (C).
[0035]
As a result of measuring an IR spectrum of the product ^{(C), ν = 1248cm -1} , a peak of P = O stretching vibration ^{1267cm -1, ν = 936cm -1,} P-N stretching vibration and 967 cm ^-1 P- There was a peak of O stretching vibration. Moreover, when DTA (differential thermal analysis) was measured, the peak considered to be melting | fusing point was observed at 207.5 degreeC and 241.6 degreeC. The 1% weight loss temperature was 209 ° C, and the 5% weight loss temperature was 296 ° C.
[0036]
About this product (C), when the gel permeation chromatography (GPC) measurement, two peaks appeared, and these were 26:74 in the peak area ratio measured with the UV (254 nm) detector.
[0037]
When each was fractionated and subjected to mass spectrometry analysis, the product (C) was represented by 74 wt% of acetoguanamine monophosphate amide (molecular weight: 357) represented by the following formula (C1) and the following formula (C2). Of acetoguanamine, which is 26% by weight (molecular weight: 589).
[0038]
[Chemical 9]

Examples 4 to 6 and Comparative Example 1
A resin was mixed with 15 parts by weight of a flame retardant using 89 parts by weight of a bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.) and 11 parts by weight of diethylenetriamine as a curing agent. Examples of the flame retardant include the product (A) of Example 1 in Example 4, the product (B) of Example 2 in Example 5, and the product (C) of Example 3 in Example 6. In Comparative Example 1, ammonium polyphosphate (trade name: Sumisafe-P, manufactured by Sumitomo Chemical Co., Ltd.) was used.
[0039]
The obtained mixture was degassed and heated at 60 ° C. for 30 minutes, and then subjected to hot pressing at 100 ° C. for 15 minutes to prepare a flat plate. The obtained flat plate was cut out to prepare a test piece having a predetermined shape, and a flame retardancy test and a water resistance test were performed. The results are shown in Table 1.
[0040]
[Table 1]

Each measuring method is as follows.
[0041]
Flame retardancy test: The oxygen index was measured according to JIS-K-7201. Moreover, the vertical combustion test (V-0-V-2) based on UL94 was done (test piece of thickness 1/8 inch).
[0042]
Water resistance test: The elution rate of the flame retardant was examined when a 2.5 cm × 2.5 cm (1/8 inch thick) test piece was immersed in warm water at 80 ° C. for 2 days.
[0043]
Examples 7 to 9 and Comparative Examples 2 and 3
Using 100 parts by weight of polypropylene (trade name: Chisso Polypro K1014, manufactured by Chisso Corporation) as a resin, 20 parts by weight of a flame retardant was blended and kneaded at 200 ° C. with a hot roll. As a flame retardant, the product (A) of Example 1 is used in Example 7, the product (B) of Example 2 is used in Example 8, and the product (C) of Example 3 is used in Example 9. In Comparative Example 2, ammonium polyphosphate (trade name: Sumisafe-P, manufactured by Sumitomo Chemical Co., Ltd.) is used. In Comparative Example 3, a nitrogen-containing organophosphorus compound of the melamine derivative represented by the following formula (D) is used. , Respectively.
[0044]
Embedded image

The obtained kneaded material was hot-pressed at 200 ° C. and 150 kg / cm ² for 3 minutes to prepare a test piece having a predetermined shape, and subjected to a flame retardancy test, a tensile test, a water resistance test, and a heat resistance test. The results are shown in Table 2.
[0045]
[Table 2]

Here, the measuring methods of the tensile test and the heat resistance test are as follows.
[0046]
Tensile test: A test piece No. 2 was used in accordance with JIS-K-7113.
[0047]
Heat resistance test: After being kept in an injection molding machine at 200 ° C. for 40 minutes, the color change was measured with a color difference meter.
[0048]
【The invention's effect】
As seen in the above examples, when the nitrogen-containing organophosphorus compound of the present invention is used by being added to a thermoplastic resin or a thermosetting resin, it is excellent in flame retardancy, water resistance, and thermal stability. In addition, a flame retardant resin having a small decrease in physical properties can be obtained.

Claims (2)

A nitrogen-containing organophosphorus compound represented by the following general formula (1).

(In the formula, m is 1 or 2, and R ¹ , R ² and R ³ are each independently a C1-C10 alkyl group, alkenyl group or cycloalkyl group, or

(Wherein R ⁷ is a C1 to C10 alkyl group, n is an integer of 0 to 3), and R ⁴ , R ⁵ , and R ⁶ are each independently hydrogen or A C1-C10 alkyl group, an alkenyl group or a cycloalkyl group; ) A flame retardant resin composition comprising a resin and the nitrogen-containing organophosphorus compound according to claim 1.