JP2011225723A - Phosphorous acid-based flame retardant, and flame-retardant resin composition - Google Patents
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本発明は、亜リン酸塩を含む亜リン酸系難燃剤、およびこのような難燃剤と樹脂とを配合してなる難燃性樹脂組成物に関するものであり、特に亜リン酸塩からのホスフィン発生を抑制した亜リン酸系難燃剤、およびこのような亜リン酸系難燃剤を配合した難燃性樹脂組成物に関するものである。 TECHNICAL FIELD The present invention relates to a phosphite-based flame retardant containing phosphite, and a flame retardant resin composition comprising such a flame retardant and a resin, and in particular, phosphine from phosphite. The present invention relates to a phosphite-based flame retardant that suppresses generation, and a flame-retardant resin composition containing such a phosphite-based flame retardant.
樹脂に難燃剤を配合することによって、樹脂の燃焼性を低減した樹脂組成物が、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野において適用されている。このような樹脂組成物に配合される難燃剤としては、赤リンを含む赤リン系難燃剤や亜リン酸塩を含む亜リン酸系難燃剤、等が知られている。例えば、特許文献１には、亜リン酸系難燃剤として用いられる亜リン酸塩の代表的なものとしての亜リン酸アルミニウムを製造するための有用な方法が提案されている。 By blending a flame retardant with a resin, a resin composition in which the flammability of the resin is reduced has been applied in various fields such as paints, adhesives, electrical and electronic parts, automobiles, and building interiors. As a flame retardant blended in such a resin composition, a red phosphorus flame retardant containing red phosphorus, a phosphorous acid flame retardant containing phosphite, and the like are known. For example, Patent Document 1 proposes a useful method for producing aluminum phosphite as a typical phosphite used as a phosphite-based flame retardant.
これらの難燃剤では、加熱時にホスフィン（ＰＨ3）が発生することが知られている。このホスフィンは人体に害を及ぼすガス状危険物質であり、米国におけるＴＬＶ[ＡＣＧＩＨ（Ａｍｅｒｉｃａｎ Ｃｏｎｆｅｒｅｎｃｅ ｏｆ Ｇｏｖｅｒｎｍｅｎｔａｌ Ｉｎｄｕｓｔｒｉａｌ Ｈｙｇｉｅｎｉｓｔｓ）が勧告している曝露限界（Ｔｈｒｅｓｈｏｌｄ Ｌｉｍｉｔ Ｖａｌｕｅｓ）]は、時間加重平均（Ｔｉｍｅ Ｗｅｉｇｈｔｅｄ Ａｖｅｒａｇｅ）で０．３ｐｐｍと定められている。 These flame retardants are known to generate phosphine (PH 3 ) during heating. This phosphine is a gaseous dangerous substance harmful to the human body, and the TLV [ACGIH (American Conferencing of Industrial Hygienists) recommended exposure threshold (Threshold Limit Values)] in the United States is a time-weighted average Ti ) Is defined as 0.3 ppm.
例えば、亜リン酸塩は、加熱によってホスフィンガスと縮合リン酸塩等を発生することが知られており（例えば、非特許文献１）、また、熱可塑性樹脂を用いた難燃性樹脂組成物については、作業性の向上などの要求から、加工成形温度を２００℃以上、ときには３００℃以上を超える温度で難燃性樹脂組成物を形成する場合が多くなっている。そのため、このような加工条件であっても、ホスフィンガスの発生が抑制されることが必要となる。 For example, phosphite is known to generate phosphine gas, condensed phosphate, and the like by heating (for example, Non-Patent Document 1), and a flame-retardant resin composition using a thermoplastic resin With respect to, due to demands such as improvement in workability, the flame-retardant resin composition is often formed at a processing molding temperature of 200 ° C. or higher, sometimes over 300 ° C. or higher. Therefore, even under such processing conditions, it is necessary to suppress the generation of phosphine gas.
しかしながら、いままで亜リン酸塩からのホスフィンガス発生に関して、低減若しくは抑制する技術については確立されておらず、亜リン酸系難燃剤を含む難燃性樹脂組成物の適用範囲が限られているのが実情である。 However, the technology for reducing or suppressing phosphine gas generation from phosphite has not been established so far, and the application range of flame retardant resin compositions containing a phosphorous acid flame retardant is limited. Is the actual situation.
一方、赤リン系難燃剤では、赤リンが室温雰囲気程度であってもホスフィンを放出して徐々に分解することが知られている（例えば、特許文献２）。こうした雰囲気で赤リンからホスフィンの発生を抑制するために、特許文献２の技術では、少なくとも１つの電子求引基に関しα位にある少なくとも１つの炭素−炭素二重結合を有する非環式脂肪族化合物を赤リンに添加する方法が提案されている。 On the other hand, it is known that red phosphorus flame retardants gradually decompose by releasing phosphine even when red phosphorus is at room temperature atmosphere (for example, Patent Document 2). In order to suppress the generation of phosphine from red phosphorus in such an atmosphere, the technique of Patent Document 2 discloses an acyclic aliphatic group having at least one carbon-carbon double bond in the α-position with respect to at least one electron-withdrawing group. Methods have been proposed for adding compounds to red phosphorus.
また、特許文献３には、粉末状赤リンの表面を、Ｚｎ，Ｔｉ，Ａｌ，Ｃｏ等の水酸化物や酸化物等の無機化合物、或は熱硬化性樹脂等で被覆することによって、赤リンの安定化を図ると共に、微粒子赤リンを除去することによって、赤リンからのホスフィン発生を抑制できることが示されている。 Patent Document 3 discloses that the surface of powdered red phosphorus is coated with an inorganic compound such as hydroxide, oxide such as Zn, Ti, Al, Co, or a thermosetting resin. It has been shown that generation of phosphine from red phosphorus can be suppressed by stabilizing phosphorus and removing particulate red phosphorus.
赤リン系難燃剤に関するこれらの技術は、室温〜２５０℃程度までの加熱処理でのホスフィンの発生を抑制することについては、有効なものといえる。しかしながら、熱可塑性樹脂に対して、作業性の向上などの要求から加工成形温度が３００℃を超えるような熱処理を行なう場合に、こうした樹脂に配合する亜リン酸系難燃剤のホスフィンの発生を抑制する技術としては、不十分である。また粉末状赤リンの表面を、Ｚｎ，Ｔｉ，Ａｌ，Ｃｏ等の水酸化物や酸化物等の無機化合物で被覆することは、赤リン系難燃剤の安定化を図るためには有効であるといえるが、亜リン酸系難燃剤ではそれほど有効であるとは言えない。 It can be said that these techniques relating to red phosphorus flame retardants are effective for suppressing the generation of phosphine in the heat treatment from room temperature to about 250 ° C. However, when heat treatment is performed on a thermoplastic resin such that the processing molding temperature exceeds 300 ° C. due to demands for improving workability, the generation of phosphine, a phosphite flame retardant contained in such a resin, is suppressed. It is insufficient as a technology to do. In addition, coating the surface of powdered red phosphorus with an inorganic compound such as a hydroxide or oxide such as Zn, Ti, Al, Co is effective for stabilizing the red phosphorus flame retardant. However, it cannot be said that the phosphorous acid flame retardant is so effective.
本発明は上記の様な事情に着目してなされたものであって、その目的は、３００℃を超えるような加熱条件であってもホスフィンの発生を効果的に抑制でき、各種分野で幅広く使用できるような亜リン酸系難燃剤、およびこのような難燃剤と樹脂とを配合してなる難燃性樹脂組成物を提供することにある。 The present invention has been made paying attention to the above-mentioned circumstances, and its purpose is to effectively suppress the generation of phosphine even under heating conditions exceeding 300 ° C., and it is widely used in various fields. An object of the present invention is to provide a phosphite-based flame retardant that can be used, and a flame-retardant resin composition comprising such a flame retardant and a resin.
上記目的を達成することのできた本発明の亜リン酸系難燃剤とは、亜リン酸塩に、ホスフィン発生低減作用を有する金属化合物を配合したものである点に要旨を有するものである。本発明の亜リン酸系難燃剤において、ホスフィン発生低減作用を有する金属化合物としては、バナジウム、鉄、ニッケル、銅、モリブデン、セリウムの酸化物、炭酸塩、水酸化物から選ばれる１種または２種以上の金属化合物などが挙げられる。また前記亜リン酸塩としては、亜リン酸アンモニウムが代表的なものとして挙げられる。 The phosphite-based flame retardant of the present invention that has achieved the above object has a gist in that a metal compound having a phosphine generation reducing action is blended with a phosphite. In the phosphorous acid flame retardant of the present invention, the metal compound having an action of reducing phosphine generation is one or two selected from vanadium, iron, nickel, copper, molybdenum, cerium oxide, carbonate, and hydroxide. Examples of the metal compound include more than seeds. A typical example of the phosphite is ammonium phosphite.
上記ホスフィン発生低減作用を有する金属化合物は、亜リン酸塩１００質量部に対して、金属化合物として０．３５〜２０質量部を配合するものであることが好ましい。 It is preferable that the metal compound having the phosphine generation reducing action is a compound containing 0.35 to 20 parts by mass as a metal compound with respect to 100 parts by mass of phosphite.
本発明の亜リン酸系難燃剤におけるホスフィン発生抑制の合格基準は、４００℃で３０分加熱したときのホスフィン発生量が、亜リン酸系難燃剤１g当り５０ｐｐｍ以下であることを目安とするが、用途や使用環境を総合的に考えて夫々の基準を設けても良く、より厳しい場合は１．５ｐｐｍ以下、更に０．３ｐｐｍ以下、逆により緩やかな場合は、１０ｐｐｍ以下、更に３０ｐｐｍ以下などと定めることができる。 The acceptance criterion for suppressing phosphine generation in the phosphorous acid flame retardant of the present invention is that the amount of phosphine generated when heated at 400 ° C. for 30 minutes is 50 ppm or less per gram of phosphorous acid flame retardant. In consideration of the application and usage environment, each standard may be set, and if it is more severe, 1.5 ppm or less, further 0.3 ppm or less, and conversely, if it is gentle, 10 ppm or less, further 30 ppm or less, etc. Can be determined.
上記のような亜リン酸系難燃剤と樹脂を配合することによって、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野で使用できる有用な難燃性樹脂組成物が得られる。 A useful flame retardant resin composition that can be used in various fields such as paints, adhesives, electrical and electronic parts, automobiles, building interiors, etc. by blending the phosphorous acid flame retardant and resin as described above. can get.
本発明では、亜リン酸塩に、ホスフィン発生低減作用を有する金属化合物を配合することによって、３００℃を超えるような加熱条件であってもホスフィンの発生を効果的に抑制することができる亜リン酸系難燃剤が実現でき、こうした亜リン酸系難燃剤を配合してなる難燃性樹脂組成物は様々な分野で使用できるものとなる。 In the present invention, by adding a metal compound having a phosphine generation reducing action to the phosphite, the phosphine can effectively suppress the generation of phosphine even under heating conditions exceeding 300 ° C. An acid flame retardant can be realized, and a flame retardant resin composition containing such a phosphorous acid flame retardant can be used in various fields.
本発明者らは、前記課題を解決するために様々な角度から検討を重ねた。ホスフィンは、酸素と反応して、次リン酸、亜リン酸およびオルトリン酸等、種々のリンのオキソ酸を生成することが知られている(前記非特許文献１の第１１７〜１１８頁)。一方、様々な物質を酸化触媒する機能を有する金属化合物も知られている（例えば、「触媒化学概論」斯波忠夫ほか共著、共立出版株式会社、第２２１〜２３１頁：「Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｅｒａｍｉｃ Ｓｏｃｉｅｔｙ Ｊａｐａｎ」 １０５［９］７７９−７８３（１９７７）等）。 The present inventors have studied from various angles in order to solve the above problems. It is known that phosphine reacts with oxygen to generate various phosphorus oxo acids such as hypophosphoric acid, phosphorous acid and orthophosphoric acid (pages 117 to 118 of Non-Patent Document 1). On the other hand, metal compounds having a function of catalyzing oxidation of various substances are also known (for example, “Introduction to Catalyst Chemistry”, Tadao Sonami et al., Kyoritsu Shuppan Co., Ltd., pp. 221-231: “Journal of the Ceramic Society Japan” 105 [9] 779-783 (1977) etc.).
本発明者らが、酸化触媒する機能を有する金属化合物について、更に検討したところ、特定の金属化合物では、亜リン酸塩化合物が加熱分解するときに発生するホスフィンの発生を抑制できることを見出し、本発明を完成した。 As a result of further investigation on the metal compound having a function of oxidizing catalyst, the present inventors have found that a specific metal compound can suppress the generation of phosphine generated when the phosphite compound is thermally decomposed. Completed the invention.
即ち、バナジウム、鉄、ニッケル、銅、モリブデン、セリウムの酸化物、炭酸塩および水酸化物から選ばれる１種または２種以上の金属化合物は、ホスフィン発生低減作用を有するものであり、これらの金属化合物を、亜リン酸塩に配合したものでは、亜リン酸塩化合物の加熱分解により発生するホスフィンの発生量を効果的に抑制できたのである。 That is, one or more metal compounds selected from vanadium, iron, nickel, copper, molybdenum, cerium oxides, carbonates and hydroxides have an action of reducing phosphine generation, and these metals When the compound was blended with phosphite, the amount of phosphine generated by thermal decomposition of the phosphite compound could be effectively suppressed.
上記金属化合物は、その１種または２種以上を配合することによって、その効果が発揮されるが、このうち好ましい化合物はニッケル、銅の酸化物、炭酸塩、水酸化物である。尚、これらの金属化合物と亜リン酸塩との配合形態については、亜リン酸塩に上記金属化合物を含有させたものや、亜リン酸塩の表面を上記金属化合物で被覆したもの、或は両方の形態を混在させたもののいずれも含むものであり、その配合状態によって、様々な形態のものが得られることになる。 The above-mentioned metal compound exhibits its effect by blending one or more of them, and preferred compounds among them are nickel, copper oxide, carbonate, and hydroxide. In addition, about the compounding form of these metal compounds and phosphites, the phosphite containing the above metal compounds, the phosphite surface coated with the above metal compounds, or Any of both forms are included, and various forms can be obtained depending on the blending state.
本発明で用いる亜リン酸塩としては、亜リン酸ナトリウム、亜リン酸カリウム、亜リン酸カルシウム、亜リン酸亜鉛、亜リン酸アンモニウム等も用いることもできるが、難燃性の観点からして最も好ましいのは、亜リン酸アルミニウムである。 As the phosphite used in the present invention, sodium phosphite, potassium phosphite, calcium phosphite, zinc phosphite, ammonium phosphite and the like can be used, but from the viewpoint of flame retardancy, Preference is given to aluminum phosphite.
亜リン酸塩と金属化合物の配合割合は、配合される原料の種類によっても多少異なるが、亜リン酸塩１００質量部に対して、金属化合物として０．３５〜２０質量部程度であることが好ましい。金属化合物の配合量が、亜リン酸塩１００質量部に対して０．３５質量部未満になると、金属化合物によるホスフィン発生抑制効果が発揮されにくくなる。また、２０質量部を超えると、相対的に亜リン酸塩の配合量が少なくなって難燃剤としての特性が発揮されにくくなる。 The blending ratio of the phosphite and the metal compound is slightly different depending on the type of raw material to be blended, but is about 0.35 to 20 parts by mass as the metal compound with respect to 100 parts by mass of the phosphite. preferable. When the compounding amount of the metal compound is less than 0.35 parts by mass with respect to 100 parts by mass of the phosphite, the phosphine generation suppressing effect by the metal compound is hardly exhibited. Moreover, when it exceeds 20 mass parts, the compounding quantity of a phosphite will decrease relatively and it will become difficult to exhibit the characteristic as a flame retardant.
本発明の亜リン酸系難燃剤におけるホスフィン発生抑制の合格基準は、４００℃で３０分加熱したときのホスフィン発生量が、亜リン酸系難燃剤１g当り５０ｐｐｍ以下を目安としている。即ち、本発明の亜リン酸系難燃剤では、４００℃に加熱したときにおいても、ホスフィン発生量は極めて低減されたものとなる。 The acceptance criteria for suppression of phosphine generation in the phosphorous acid flame retardant of the present invention is that the amount of phosphine generated when heated at 400 ° C. for 30 minutes is 50 ppm or less per gram of phosphorous acid flame retardant. That is, in the phosphorous acid flame retardant of the present invention, even when heated to 400 ° C., the amount of phosphine generated is extremely reduced.
上記のような亜リン酸系難燃剤と樹脂を配合することによって、塗料、接着剤、電気電子部品、自動車、建築物内装品等、様々な分野で使用できる有用な難燃性樹脂組成物が得られるのであるが、用いられる樹脂としては、ポリカーボネート樹脂、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、オレフィン樹脂、スチレン樹脂、ポリオレフィンオキシド樹脂、ビニル樹脂等の熱可塑性樹脂が挙げられる。 A useful flame retardant resin composition that can be used in various fields such as paints, adhesives, electrical and electronic parts, automobiles, building interiors, etc. by blending the phosphorous acid flame retardant and resin as described above. Although obtained, examples of the resin used include thermoplastic resins such as polycarbonate resin, acrylic resin, polyester resin, polyamide resin, olefin resin, styrene resin, polyolefin oxide resin, and vinyl resin.
以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.
［実施例１］
（１）原料の亜リン酸アルミニウムの調製
まず特許文献１に示された方法によって、亜リン酸アルミニウムを調製した。即ち、５０℃以上に加熱した４０％亜リン酸２水素アルモニウム水溶液１０００ｇに、含水水酸化アルミニウム１６１．２ｇを添加して反応させて得られた粘稠な亜リン酸アルミニウムスラリーを、５０〜９０℃で撹拌しながら微細な結晶を徐々に析出させて球状結晶に成長させて粉末状の亜リン酸アルミニウムを得た。
[Example 1]
(1) Preparation of raw material aluminum phosphite First, aluminum phosphite was prepared by the method disclosed in Patent Document 1. That is, the viscous aluminum phosphite slurry obtained by adding 161.2 g of hydrous aluminum hydroxide to 1000 g of 40% aluminum dihydrogen phosphite aqueous solution heated to 50 ° C. or more and reacting with it was mixed with 50 to 90%. While stirring at ℃, fine crystals were gradually precipitated to grow into spherical crystals to obtain powdered aluminum phosphite.
（２）亜リン酸アルミニウムと金属化合物との混合物の調製
亜リン酸アルミニウムと金属化合物との混合物の調製は、湿式または乾式のいずれも採用できるが、この実施例では亜リン酸アルミニウム１００質量部と下記表１に示した各種金属化合物を所定の割合で混合して各種難燃剤を得た（下記表１の難燃剤Ｎｏ．１〜１５）。こうして得られた難燃剤は、亜リン酸アルミニウム粉末の表面が、金属化合物によって被覆された状態になっているものと考えられた。
(2) Preparation of mixture of aluminum phosphite and metal compound Preparation of the mixture of aluminum phosphite and metal compound can be either wet or dry, but in this example 100 parts by weight of aluminum phosphite And various metal compounds shown in the following Table 1 were mixed at a predetermined ratio to obtain various flame retardants (flame retardant Nos. 1 to 15 in Table 1 below). It was considered that the flame retardant thus obtained had the surface of the aluminum phosphite powder coated with a metal compound.
（３）ホスフィン発生量の測定
上記の方法で調製した各種難燃剤について、日本燃焼剤協会リン部会に示されている方法に従ってホスフィン発生量を測定した。即ち、下記（ａ）〜（ｃ）の手順（変更点）以外は、ＪＩＳＣ３６６６−２の「電気ケーブルの燃焼時発生ガス試験方法」に準拠し、ホスフィン発生量（試料１g当りの発生濃度）を測定した。
（ａ）燃焼管を出た後に、ガラスウールを設置し、燃焼時に発生する煤を除去した。
（ｂ）乾燥剤として、シリカゲルの代りに塩化カルシウムを使用した。
（ｃ）発生ガスをテドラバッグで直接サンプリングし、検知管でホスフィン濃度を測定した。
尚、各試料は約０．３gを秤量し、４００℃に加熱した空気気流中で３分間ガスサンプリングを行い、採取した気体をホスフィン用検知管で測定した。また、このとき検知管は、ガステック社製のものを用いた（商品名：「Ｎｏ．７」、「Ｎｏ．７Ｌ」および「Ｎｏ．７ＬＡ」）。
(3) Measurement of phosphine generation amount With respect to various flame retardants prepared by the above method, the phosphine generation amount was measured in accordance with the method shown in the Japan Combustors Association phosphorus section. That is, except for the following procedures (a) to (c) (changed points), the amount of phosphine generated (generated concentration per gram of sample) is determined in accordance with “Testing method for gas generated during combustion of electric cables” of JISC3666-2. It was measured.
(A) After leaving the combustion tube, glass wool was installed to remove soot generated during combustion.
(B) Calcium chloride was used as a desiccant instead of silica gel.
(C) The generated gas was directly sampled with a Tedra bag, and the phosphine concentration was measured with a detector tube.
Each sample weighed about 0.3 g, was subjected to gas sampling in an air stream heated to 400 ° C. for 3 minutes, and the collected gas was measured with a phosphine detector tube. At this time, the detector tube manufactured by Gastec was used (trade names: “No. 7”, “No. 7L”, and “No. 7LA”).
その結果（ホスフィン発生量）を、配合した金属化合物の種類および配合量と共に下記表１に示す。 The results (phosphine generation amount) are shown in Table 1 below together with the type and amount of the compounded metal compound.
この結果から明らかなように、本発明で特定する金属化合物を配合した難燃剤（難燃剤Ｎｏ.１〜１５）では、ホスフィンガス発生量が効果的に低減されていることが分かる。 As is apparent from this result, it is understood that the amount of phosphine gas generated is effectively reduced in the flame retardant (flame retardant No. 1-15) containing the metal compound specified in the present invention.
［実施例２］
各種金属化合物を、亜リン酸アルミニウムを調製する段階で添加し、その形態による効果の違いについて確認した。まず反応一段目の第１亜リン酸アルミニウム水溶液に、下記表２の難燃剤Ｎｏ.１６〜１９に示した金属化合物を添加し、水溶液に対して十分に分散または溶解させた。これと、水酸化アルミニウムスラリーとを反応させ、亜リン酸アルミニウムを得た。得られた亜リン酸アルミニウムは、金属化合物を含有および／または被覆した状態になっているものと考えられた。
[Example 2]
Various metal compounds were added at the stage of preparing aluminum phosphite, and the difference in effect depending on the form was confirmed. First, the metal compounds shown in flame retardant Nos. 16 to 19 in Table 2 below were added to the first aqueous aluminum phosphite aqueous solution in the first stage of the reaction, and were sufficiently dispersed or dissolved in the aqueous solution. This was reacted with an aluminum hydroxide slurry to obtain aluminum phosphite. It was considered that the obtained aluminum phosphite contained and / or coated a metal compound.
また水酸化アルミニウムスラリーに、下記表２、３の難燃剤Ｎｏ.２１〜３５に示した金属化合物を添加し、これと反応一段目の第１亜リン酸アルミニウム水溶液とを反応させ、亜リン酸アルミニウムを得た。得られた亜リン酸アルミニウムは、金属化合物を被覆した状態になっているものと考えられた。 Moreover, the metal compound shown to flame retardant No. 21-35 of following Table 2, 3 is added to an aluminum hydroxide slurry, this is made to react with the 1st aluminum phosphite aqueous solution of the 1st reaction stage, and phosphorous acid Aluminum was obtained. The obtained aluminum phosphite was considered to be in a state of being coated with a metal compound.
上記で得られた各種難燃剤（難燃剤Ｎｏ.１６〜３５）について、実施例１と同様にしてホスフィン発生量を測定した。その結果（ホスフィン発生量）を、混合した金属化合物の種類および配合量と共に下記表２、３に示す。尚、下記表２に示した難燃剤Ｎｏ．２０の例は、金属化合物を配合していない亜リン酸アルミニウム単体のものである。また、表２に示した、ホスフィン発生量が「＜０．１」は測定限界以下であることを示している。 About the various flame retardants obtained above (flame retardants Nos. 16 to 35), the amount of phosphine generated was measured in the same manner as in Example 1. The results (phosphine generation amount) are shown in Tables 2 and 3 below together with the type and blending amount of the mixed metal compound. In addition, the flame retardant No. shown in Table 2 below. The example of 20 is a thing of the aluminum phosphite single-piece | unit which is not mix | blending a metal compound. In Table 2, the amount of phosphine generation “<0.1” indicates that it is below the measurement limit.
この結果から明らかなように、本発明で規定する金属化合物を配合した難燃剤（難燃剤Ｎｏ.１６〜１９、２１〜２７）では、ホスフィンガス発生量が効果的に低減されていることが分かる。これに対して、金属化合物を配合していないもの（難燃剤Ｎｏ.２０）や本発明で規定する以外の金属化合物を配合した難燃剤（難燃剤Ｎｏ.２８〜３５）では、ホスフィンガス発生量が効果的に低減されていないことが分かる。 As is clear from this result, it is understood that the amount of phosphine gas generated is effectively reduced in the flame retardant (flame retardants Nos. 16-19 and 21-27) containing the metal compound defined in the present invention. . On the other hand, the amount of phosphine gas generated in a flame retardant (flame retardant No. 28 to 35) containing no metal compound (flame retardant No. 20) or a metal compound other than those prescribed in the present invention. It can be seen that is not effectively reduced.
［実施例３］
上記表１〜３に示した各種難燃剤（難燃剤Ｎｏ.１〜３５）について、ポリカーボネート樹脂(「ユーピロンＳ−２０００」（商品名） 三菱エンジニアリングプラスチック社製)１００質量部に対して、難燃剤２０質量部となるように混合し、混合機にて混練し、熱間プレスを用いて厚さ４ｍｍのＵＬ−９４試験片を作製した。この試験片を用いてＵＬ−９４による燃焼性試験を行なった。このＵＬ−９４による燃焼性試験は、規定された寸法の試験片にバーナの炎を当てて試験片の燃焼の程度を調査するものであり、難燃性の等級として、５ＶＡ、５ＶＢ、Ｖ−０、Ｖ−１、Ｖ−２、ＨＢ(難燃性の高いものから順に)に区別されている。
[Example 3]
About various flame retardants (flame retardant No. 1-35) shown in the said Tables 1-3, a flame retardant with respect to 100 mass parts of polycarbonate resin ("Iupilon S-2000" (brand name) Mitsubishi engineering plastic company make). It mixed so that it might become 20 mass parts, knead | mixed with the mixer, and produced the UL-94 test piece of thickness 4mm using the hot press. Using this test piece, a flammability test by UL-94 was conducted. In this flammability test according to UL-94, a burner flame is applied to a test piece of a prescribed size to investigate the degree of combustion of the test piece. As the flame retardancy rating, 5VA, 5VB, V- 0, V-1, V-2, and HB (in order of increasing flame retardancy).
本発明においては、上記等級でＶ−２以上を合格とした。その結果を、用いた難燃剤の種類と共に、下記表４、５に示す。 In the present invention, V-2 or higher was regarded as acceptable in the above grade. The results are shown in Tables 4 and 5 below together with the type of flame retardant used.
この結果から、次のように考察できる。まず実験Ｎｏ．１〜１９のものでは、難燃剤における亜リン酸塩の配合量が適切な範囲にあるので、良好な難燃性を示していることが分かる。これに対し、実験Ｎｏ．２１〜２７のものでは、難燃剤中の金属化合物の配合量が多くなっており（相対的に亜リン酸アルミニウムの配合量が少なくなっている）、良好な難燃性が発揮されていないことが分かる。また、実験Ｎｏ．２８〜３５のものでは、本発明で規定する金属化合物以外の金属化合物を配合したものであるが、このうち実験Ｎｏ．３２〜３５のものは難燃性に関しては良好な結果が得られている。 From this result, it can be considered as follows. First, experiment no. In the case of Nos. 1 to 19, since the blending amount of the phosphite in the flame retardant is in an appropriate range, it can be seen that good flame retardancy is exhibited. In contrast, Experiment No. In 21 to 27, the compounding amount of the metal compound in the flame retardant is large (relatively the compounding amount of aluminum phosphite is relatively small), and good flame retardancy is not exhibited. I understand. In addition, Experiment No. In the case of 28 to 35, a metal compound other than the metal compound specified in the present invention was blended. The thing of 32-35 has acquired the favorable result regarding the flame retardance.
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| KR20140107392A (en) * | 2011-12-05 | 2014-09-04 | 클라리언트 파이넌스 (비브이아이)리미티드 | Mixtures of aluminium hydrogenphosphites with aluminium salts, process for the production thereof and the use thereof |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| LAPS | Cancellation because of no payment of annual fees |