JP2004155802A - Flame-retardant resin composition - Google Patents
Flame-retardant resin composition Download PDFInfo
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- JP2004155802A JP2004155802A JP2002313724A JP2002313724A JP2004155802A JP 2004155802 A JP2004155802 A JP 2004155802A JP 2002313724 A JP2002313724 A JP 2002313724A JP 2002313724 A JP2002313724 A JP 2002313724A JP 2004155802 A JP2004155802 A JP 2004155802A
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- phenoxyphosphazene
- resin
- flame
- resin composition
- resins
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- 239000011342 resin composition Substances 0.000 title abstract description 12
- 239000003063 flame retardant Substances 0.000 title description 17
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title description 11
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 230000014759 maintenance of location Effects 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 9
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000002411 thermogravimetry Methods 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- -1 phenoxy phosphazene Chemical compound 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229920001955 polyphenylene ether Polymers 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、環境面で好ましい難燃性樹脂組成物に関する。
【０００２】
【従来の技術】従来、難燃性樹脂組成物用難燃剤としては、ハロゲン系化合物、水酸化化合物、燐系化合物、窒素系化合物などが使用されてきている。
近年、環境問題から、非ハロゲン難燃剤への要求が強くハロゲン元素を分子内に含まない各種難燃剤が検討されている。その中で、燐系難燃剤はその難燃化効果が多くの樹脂に対して認められることもあり、有力候補である。
燐系難燃剤としては、赤燐、燐酸エステル、縮合燐酸エステルなどが実用に供されているが、いずれも問題を抱えていた。赤燐は、水分と熱の影響でフォスフィンを発生することによる毒性問題や、金属腐食を引き起こす問題、燐酸エステル、縮合リン酸エステルは、燐含有率が高くないので、添加量が多く必要でそのため機械的物性、熱的物性が下がったり、コストが高くなったりする問題があった。
【０００３】
近年、ホスファゼン系化合物が、燐含有率が高いこともあって、注目されてきている。中でもフェノキシホスファゼンがその高い耐熱性、耐加水分解性、難燃性によって高い評価を受けている（例えば、特許文献１〜５参照。）。しかし、フェノキシホスファゼンは、その製法から一般に、重合度の異なる環状物、鎖状物の混合物として得られ、また、Ｐに結合した置換基全てが必ずしもフェノキシ置換基でないものが得られ、樹脂に添加した場合に難燃化効果が著しく劣ったり、熱可塑性樹脂に添加した場合は成形流動性を著しく低下させるフェノキシホスファゼンが存在し、フェノキシホスファゼンの有用性を著しくそこねていた。
【０００４】
【特許文献１】
特公平３−７３５９０号公報
【特許文献２】
特開平９−７１７０８号公報
【特許文献３】
特開平８−２２５７１４号公報
【特許文献４】
ＷＯ９９−１９３８３号明細書
【特許文献５】
ＰＣＴ−ＪＰ０１／７６１０号明細書
【０００５】
【発明が解決しようとする課題】
フェノキシホスファゼンであって、樹脂に添加した場合、高い難燃化効果を示し、かつ熱可塑性樹脂に添加した場合は、良好な成形流動性を示すフェノキシホスファゼンを添加した樹脂組成物を示すことにある。
【０００６】
【課題を解決するための手段】
難燃性に優れ、熱可塑性樹脂に添加した場合、成形流動性にも優れた特性を安定して示すフェノキシホスファゼンを得るべく鋭意検討した結果、フェノキシホスファゼンであって、式（１）を有する環状フェノキシホスファゼンを８０ｗｔ％以上含有しており、ＴＧＡによる、不活性ガス雰囲気中、昇温速度１０℃／ｍｉｎで、常温から６００℃まで加熱した時の、５００℃における重量保持率が、１０％以下であることを特徴とするフェノキシホスファゼンと樹脂からなる組成物が、難燃性、成形流動性ともに安定して優れる組成物であることを見出し、本発明に至った。
【０００７】
【化４】
以下本発明を詳細に説明する。
本発明に用いられるフェノキシホスファゼンは、式（１）を有する環状フェノキシホスファゼンを８０ｗｔ％以上含有しており、ＴＧＡによる不活性ガス雰囲気中、昇温速度１０℃／ｍｉｎで、常温から６００℃まで加熱した時の５００℃における重量保持率が、１０％以下であることを特徴とするフェノキシホスファゼンと樹脂からなる組成物である。
【０００９】
【化５】
ホスファゼン化合物は、公知の化合物であり、例えばＪａｍｅｓ Ｅ．Ｍａｒｋ，Ｈａｒｒｙ Ｒ． Ａｌｌｃｏｃｋ，Ｒｏｂｅｒｔ Ｗｅｓｔ著、“Ｉｎｏｒｇａｎｉｃ Ｐｏｌｙｍｅｒｓ”Ｐｒｅｔｉｃｅ−Ｈａｌｌ Ｉｎｔｅｒｎａｔｉｏｎａｌ，Ｉｎｃ．， １９９２， ｐ６１−ｐ１４０に記載されている。これらホスファゼン化合物を得るための参考文献および合成例は、特公平３−７３５９０号公報、特開平９−７１７０８号公報、特開平９−１８３８６４号公報および特開平１１−１８１４２９号公報等に開示されている。
【００１１】
本発明において、樹脂は、一般に工業的に生産・使用されている樹脂であって、熱可塑性樹脂、熱硬化性樹脂を含む。
熱可塑性樹脂としては、ポリフェニレンエーテル、ポリカーボネート、ポリアミド、ポリエステル、ＡＢＳ、ポリスチレン、ＨＩＰＳ、ポリエチレン、ポリプロピレン、など工業的に供されている樹脂及びこれら樹脂２以上を混合して得られる樹脂が挙げられる。
【００１２】
熱硬化性樹脂としては、エポキシ樹脂、フェノール樹脂、メラミン樹脂など工業的に供されている樹脂及びこれら樹脂２以上を混合して得られる樹脂が挙げられる。
熱硬化性樹脂と熱可塑性樹脂を混合して得られる樹脂も使用しうる。
フェノキシホスファゼンと樹脂との配合比は、難燃性が発現するために必要なフェノキシホスファゼン配合量を添加すれば良い。フェノキシホスファゼンと樹脂の合計量１００重量部に対して、フェノキシホスファゼン添加量は１〜５０重量部、好ましくは、３〜４０重量部、さらに好ましくは５〜３０重量部である。
【００１３】
本発明の樹脂組成物には、一般に樹脂に添加される添加剤を添加することができる。例えば、ガラス繊維、ガラスフレーク、カオリンクレー、タルク、マイカ等の無機充填剤やその他の繊維状、非繊維状補強剤。また、耐衝撃付与剤としてゴム状重合体、例えばスチレン−ブタジエンブロック共重合体、スチレン−イソプレンブロック共重合体およびそれらの水素添加物などの熱可塑性エラストマー。更に他の特性を付与するため、または本発明の効果を損なわない範囲で他の添加剤、例えば可塑剤、酸化防止剤、及び紫外線吸収剤などの安定剤、帯電防止剤、離型剤、染顔料、あるいはその他の樹脂を添加することができる。また、従来から知られた各種難燃剤および難燃助剤、例えば結晶水を含有する水酸化マグネシウムや水酸化アルミニウム等のアルカリ金属水酸化物またはアルカリ土類金属水酸化物、ホウ酸亜鉛化合物、スズ酸亜鉛化合物、さらにはシリカ、カオリンクレー、タルクなどの無機ケイ素化合物を添加して更なる難燃性の向上も可能である。
【００１４】
本発明の樹脂組成物の製造方法は、特に限定するものではない。熱可塑性樹脂においては、２軸押出機、１軸押出機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて混練製造することができる。その中でも押出機による混合が、生産性の面で好ましい。混合温度は、ベース樹脂の好ましい加工温度に従えばよい。熱硬化性樹脂においては、溶媒に溶解して樹脂原料、硬化剤、硬化促進剤、難燃剤などを混合し、加熱硬化反応、乾燥を行う方法、溶媒を使用せず同様の反応を行う方法などが挙げられる。
【００１５】
【発明の実施の形態】
以下、実施例によって本発明を具体的に説明するが、本発明は以下の例に限定されるものではない。
実施例および比較例で用いた各成分は以下のものである。
・ポリフェニレンエーテル（ＰＰＥ）
３０℃のクロロホルム溶液で測定したηｓｐ／ｃが０．５４のポリ−２，６−ジメチル−１，４−フェニレンエーテル。
・ゴム補強ポリスチレン（ＨＩＰＳ）
ゴム含量９％、３０℃、トルエン溶液で測定したマトリックスポリスチレンのηｓｐ／ｃが０．６４、体積平均ゴム粒子径が１．５μｍのゴム補強ポリスチレン。
・フェノキシホスファゼン化合物
６員環および８員環を主成分とするクロロホスファゼン混合物とカリュウムフェノラートを反応して得られたフェノキシホスファゼン合成物。
その構成成分及び特性の異なる９種類のフェノキシホスファゼンについて評価した。（ＦＲ１〜ＦＲ９；各々の構成成分比、特性を表１、表２に示した。）
【００１６】
実施例および比較例の難燃剤のＴＧＡ及び樹脂組成物の難燃性、流動性は、以下の方法及び条件で行った。
（１）ＴＧＡ
難燃剤１０ｍｇを、パーキンエルマー社製Ｔｈｅｒｍａｌ Ａｎａｌｙｓｉｓ Ｓｙｓｔｅｍ ７ Ｓｅｒｉｅｓを用いて、窒素気流３０ｍｌ／ｍｉｎ中、１０℃／ｍｉｎの速度で６００℃まで昇温したとき、５００℃における重量を１００℃における重量で除して１００を乗じた値を、５００℃における重量保持率として表１および２に記載した。
（２）難燃性
ＵＬ−９４ 垂直燃焼試験に基づき、１／１６インチ厚みの射出成形試験片を用いて測定し、１０回接炎時の平均燃焼時間と燃焼時の滴下物による脱脂綿着火の有無を評価した。
（３）ＭＦＲ
ＪＩＳ Ｋ７２１０に従って測定した。
【００１７】
【実施例１〜１０、比較例１】
各成分を下記に示す割合で混合し、加熱シリンダーの最高温度を３００℃に設定したスクリュー直径２５ｍｍの二軸押出機に供給して、スクリュー回転数３００ｒｐｍで溶融混合し、ストランドを冷却裁断して樹脂組成物ペレットを得た。次に、得られた樹脂組成物ペレットを、射出成形により２４０〜２９０℃にて物性試験片を成形し、上記試験法により物性試験を行い、表１、２の結果を得た。
【００１８】
＜成分組成＞
実施例１〜５：ＰＰＥ／ＨＩＰＳ／フェノキシホスファゼン化合物＝５５／３３／１２（重量部）
実施例６〜１０および比較例１：ＰＰＥ／ＨＩＰＳ／フェノキシホスファゼン化合物＝４０／４５／１５（重量部）
Ｃ３、Ｃ４およびＣ５以上の意味
Ｃ３：化学式（１）において、ｍ＝３である６員環の環状フェノキシホスファゼン
Ｃ４：化学式（１）において、ｍ＝４である８員環の環状フェノキシホスファゼン
Ｃ５以上：化学式（１）において、ｍ＝５である１０員環環状フェノキシホスファゼン及びｍ≧６である、１２員環以上の多員環環状フェノキシホスファゼン
【００１９】
【表１】
【表２】
【発明の効果】
本発明は、ハロゲンを含まず、難燃性に優れ、射出成形時の発煙、金型への難燃剤の付着等の問題点がない環境上好ましい、高度の難燃性を有する樹脂組成物を提供する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an environmentally preferable flame-retardant resin composition.
[0002]
2. Description of the Related Art Heretofore, halogen-based compounds, hydroxide compounds, phosphorus-based compounds, nitrogen-based compounds and the like have been used as flame retardants for flame-retardant resin compositions.
In recent years, due to environmental issues, there has been a strong demand for non-halogen flame retardants, and various flame retardants that do not contain halogen elements in their molecules have been studied. Among them, a phosphorus-based flame retardant is a promising candidate, because its flame retardant effect is recognized for many resins.
As phosphorus-based flame retardants, red phosphorus, phosphate esters, condensed phosphate esters and the like have been put to practical use, but all have had problems. Red phosphorus is a toxic problem due to the generation of phosphine under the influence of moisture and heat, a problem of causing metal corrosion, phosphate esters and condensed phosphate esters do not have a high phosphorus content, so a large amount of addition is necessary, so There have been problems that mechanical and thermal properties are reduced and costs are increased.
[0003]
In recent years, phosphazene-based compounds have been receiving attention due to their high phosphorus content. Among them, phenoxyphosphazene has been highly evaluated for its high heat resistance, hydrolysis resistance, and flame retardancy (for example, see Patent Documents 1 to 5). However, phenoxyphosphazene is generally obtained from its production method as a mixture of cyclic and chain products having different degrees of polymerization, and all of the substituents bonded to P are not necessarily phenoxy substituents. In this case, there is phenoxyphosphazene which significantly deteriorates the flame-retardant effect, or when added to a thermoplastic resin, significantly reduces the molding fluidity, which significantly impairs the usefulness of phenoxyphosphazene.
[0004]
[Patent Document 1]
Japanese Patent Publication No. 3-73590 [Patent Document 2]
Japanese Patent Application Laid-Open No. 9-71708 [Patent Document 3]
JP-A-8-225714 [Patent Document 4]
WO99-19383 [Patent Document 5]
PCT-JP01 / 7610 specification
[Problems to be solved by the invention]
A phenoxyphosphazene, which, when added to a resin, exhibits a high flame-retardant effect, and when added to a thermoplastic resin, refers to a resin composition to which phenoxyphosphazene having good molding fluidity is added. .
[0006]
[Means for Solving the Problems]
As a result of intensive studies to obtain a phenoxyphosphazene having excellent flame retardancy and stable molding fluidity when added to a thermoplastic resin, a phenoxyphosphazene which is a cyclic compound having the formula (1) Contains 80% by weight or more of phenoxyphosphazene, and has a weight retention of 10% or less at 500 ° C. when heated from normal temperature to 600 ° C. at a rate of 10 ° C./min in an inert gas atmosphere by TGA. The present inventors have found that a composition comprising phenoxyphosphazene and a resin, characterized by the following, is a composition that is stably excellent in both flame retardancy and molding fluidity, and has led to the present invention.
[0007]
Embedded image
Hereinafter, the present invention will be described in detail.
The phenoxy phosphazene used in the present invention contains at least 80 wt% of the cyclic phenoxy phosphazene having the formula (1), and is heated from normal temperature to 600 ° C. in an inert gas atmosphere by TGA at a heating rate of 10 ° C./min. A composition comprising a phenoxyphosphazene and a resin, wherein a weight retention at 500 ° C. when performed is 10% or less.
[0009]
Embedded image
The phosphazene compound is a known compound, for example, James E.P. Mark, Harry R. Allcock, Robert West, "Inorganic Polymers," Precision-Hall International, Inc. , 1992, p61-p140. References and synthesis examples for obtaining these phosphazene compounds are disclosed in JP-B-3-73590, JP-A-9-71708, JP-A-9-183864 and JP-A-11-181429. I have.
[0011]
In the present invention, the resin is a resin generally produced and used industrially, and includes a thermoplastic resin and a thermosetting resin.
Examples of the thermoplastic resin include polyphenylene ether, polycarbonate, polyamide, polyester, ABS, polystyrene, HIPS, polyethylene, polypropylene, and other industrially available resins, and resins obtained by mixing two or more of these resins.
[0012]
Examples of the thermosetting resin include epoxy resins, phenol resins, melamine resins, and other industrially available resins, and resins obtained by mixing two or more of these resins.
Resins obtained by mixing a thermosetting resin and a thermoplastic resin can also be used.
The compounding ratio of phenoxyphosphazene and resin may be determined by adding a compounding amount of phenoxyphosphazene necessary for developing flame retardancy. The amount of phenoxyphosphazene added is 1 to 50 parts by weight, preferably 3 to 40 parts by weight, and more preferably 5 to 30 parts by weight, based on 100 parts by weight of the total amount of phenoxyphosphazene and resin.
[0013]
Additives generally added to resins can be added to the resin composition of the present invention. For example, inorganic fillers such as glass fiber, glass flake, kaolin clay, talc, and mica, and other fibrous and non-fibrous reinforcing agents. In addition, thermoplastic elastomers such as rubbery polymers, for example, styrene-butadiene block copolymers, styrene-isoprene block copolymers, and hydrogenated products thereof as impact modifiers. In order not to impair the effects of the present invention or to impart other properties, other additives such as a stabilizer such as a plasticizer, an antioxidant, and an ultraviolet absorber, an antistatic agent, a release agent, and a dye Pigments or other resins can be added. Further, conventionally known various flame retardants and flame retardant assistants, for example, alkali metal hydroxides or alkaline earth metal hydroxides such as magnesium hydroxide and aluminum hydroxide containing water of crystallization, zinc borate compounds, Addition of a zinc stannate compound and further an inorganic silicon compound such as silica, kaolin clay, and talc can further improve flame retardancy.
[0014]
The method for producing the resin composition of the present invention is not particularly limited. The thermoplastic resin can be manufactured by kneading using a kneader such as a twin-screw extruder, a single-screw extruder, a heating roll, a kneader, and a Banbury mixer. Among them, mixing by an extruder is preferable in terms of productivity. The mixing temperature may be in accordance with the preferred processing temperature of the base resin. For thermosetting resin, a method of dissolving in a solvent, mixing a resin raw material, a curing agent, a curing accelerator, a flame retardant, and the like, performing a heat curing reaction, drying, a method of performing a similar reaction without using a solvent, and the like Is mentioned.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to the following Examples.
The components used in the examples and comparative examples are as follows.
・ Polyphenylene ether (PPE)
Poly-2,6-dimethyl-1,4-phenylene ether having an ηsp / c of 0.54 measured in a chloroform solution at 30 ° C.
・ Rubber reinforced polystyrene (HIPS)
Rubber reinforced polystyrene having a rubber content of 9%, ηsp / c of matrix polystyrene measured in a toluene solution at 30 ° C. of 0.64, and a volume average rubber particle diameter of 1.5 μm.
Phenoxyphosphazene compound A phenoxyphosphazene compound obtained by reacting a chlorophosphazene mixture mainly composed of a 6-membered ring and an 8-membered ring with calium phenolate.
Nine kinds of phenoxyphosphazenes having different constituent components and characteristics were evaluated. (FR1 to FR9; the ratios and characteristics of the respective constituent components are shown in Tables 1 and 2.)
[0016]
The TGA of the flame retardants of Examples and Comparative Examples and the flame retardancy and fluidity of the resin compositions were measured by the following methods and conditions.
(1) TGA
When 10 mg of the flame retardant was heated to 600 ° C. at a rate of 10 ° C./min in a nitrogen gas flow of 30 ml / min using Thermal Analysis System 7 Series manufactured by PerkinElmer, the weight at 500 ° C. was reduced to the weight at 100 ° C. The values obtained by dividing by 100 and multiplying by 100 are shown in Tables 1 and 2 as the weight retention at 500 ° C.
(2) Flame retardancy Based on UL-94 vertical burning test, measured using an injection molded test piece having a thickness of 1/16 inch, the average burning time after 10 times of flame contact and the ignition of absorbent cotton by dripping material during burning The presence or absence was evaluated.
(3) MFR
It was measured according to JIS K7210.
[0017]
Examples 1 to 10, Comparative Example 1
The respective components were mixed in the ratio shown below, and supplied to a twin-screw extruder having a screw diameter of 25 mm in which the maximum temperature of the heating cylinder was set at 300 ° C., melt-mixed at a screw rotation speed of 300 rpm, and cooled and cut the strand. A resin composition pellet was obtained. Next, physical properties test pieces were molded from the obtained resin composition pellets at 240 to 290 ° C. by injection molding, and physical properties tests were performed by the above-described test methods. The results shown in Tables 1 and 2 were obtained.
[0018]
<Component composition>
Examples 1 to 5: PPE / HIPS / phenoxyphosphazene compound = 55/33/12 (parts by weight)
Examples 6 to 10 and Comparative Example 1: PPE / HIPS / phenoxyphosphazene compound = 40/45/15 (parts by weight)
C3, C4 and the meaning of C5 or more C3: 6-membered cyclic phenoxyphosphazene in which m = 3 in the chemical formula (1) C4: 8-membered cyclic phenoxyphosphazene C5 or more in which m = 4 in the chemical formula (1) In the formula (1), a 10-membered cyclic phenoxyphosphazene in which m = 5 and a 12- or more-membered multicyclic phenoxyphosphazene in which m ≧ 6.
[Table 1]
[Table 2]
【The invention's effect】
The present invention provides a resin composition having a high level of flame retardancy, which does not contain halogen, has excellent flame retardancy, does not have problems such as smoke during injection molding and adhesion of a flame retardant to a mold. provide.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| JP2002313724A JP2004155802A (en) | 2002-09-13 | 2002-10-29 | Flame-retardant resin composition |
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| JP2002268112 | 2002-09-13 | ||
| JP2002313724A JP2004155802A (en) | 2002-09-13 | 2002-10-29 | Flame-retardant resin composition |
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| JP2004155802A true JP2004155802A (en) | 2004-06-03 |
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| WO2006043460A1 (en) * | 2004-10-18 | 2006-04-27 | Asahi Kasei Chemicals Corporation | Flame retardant composition |
| WO2014086944A1 (en) | 2012-12-07 | 2014-06-12 | Bayer Materialscience Ag | Flame-retardant polycarbonate molding materials ii |
| JP2014145066A (en) * | 2013-01-30 | 2014-08-14 | Sekisui Plastics Co Ltd | Flame-retardant styrene resin particle and method for producing the same, foamable particle, foaming particle, and formed-molded body |
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| JP2015537100A (en) * | 2012-12-07 | 2015-12-24 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flameproof polycarbonate molding compound III |
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| WO2006043460A1 (en) * | 2004-10-18 | 2006-04-27 | Asahi Kasei Chemicals Corporation | Flame retardant composition |
| US7759418B2 (en) | 2004-10-18 | 2010-07-20 | Asahi Kasei Chemicals Corporation | Flame retardant resin composition |
| WO2014086944A1 (en) | 2012-12-07 | 2014-06-12 | Bayer Materialscience Ag | Flame-retardant polycarbonate molding materials ii |
| JP2015537100A (en) * | 2012-12-07 | 2015-12-24 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flameproof polycarbonate molding compound III |
| JP2016501302A (en) * | 2012-12-07 | 2016-01-18 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flame retardant polycarbonate molding composition V |
| JP2016501300A (en) * | 2012-12-07 | 2016-01-18 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flame Retardant Polycarbonate Molding Composition IV |
| JP2016501304A (en) * | 2012-12-07 | 2016-01-18 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flameproof polycarbonate molding compound II |
| JP2016501298A (en) * | 2012-12-07 | 2016-01-18 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Flame retardant polycarbonate molding composition I |
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