JPS63118368A - Flame-retardant polyamide composition - Google Patents
Flame-retardant polyamide compositionInfo
- Publication number
- JPS63118368A JPS63118368A JP26493186A JP26493186A JPS63118368A JP S63118368 A JPS63118368 A JP S63118368A JP 26493186 A JP26493186 A JP 26493186A JP 26493186 A JP26493186 A JP 26493186A JP S63118368 A JPS63118368 A JP S63118368A
- Authority
- JP
- Japan
- Prior art keywords
- flame
- halogenated bisphenol
- polyamide composition
- formula
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000003063 flame retardant Substances 0.000 title claims description 13
- 239000004952 Polyamide Substances 0.000 title claims description 11
- 229920002647 polyamide Polymers 0.000 title claims description 11
- 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 claims description 10
- 238000002156 mixing Methods 0.000 claims abstract 3
- 125000003700 epoxy group Chemical group 0.000 claims abstract 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract 2
- -1 halogenated bisphenol compound Chemical class 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 229920001007 Nylon 4 Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract description 2
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 2
- 229920003189 Nylon 4,6 Polymers 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 125000002947 alkylene group Chemical group 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 239000004677 Nylon Substances 0.000 description 7
- 229920001778 nylon Polymers 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 229920001955 polyphenylene ether Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
ａ産業上の利用分野
本発明は、耐衝撃性、成形品外観及びウェルド強度の改
良された難燃性ポリアミド組成物に関する。DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a flame-retardant polyamide composition with improved impact resistance, molded article appearance and weld strength.
ｂ従来技術
該分野において、米国のＵＬ規格に基づく高い難燃性が
要求され、各種難燃性組成物が提案されている。B. Prior Art In this field, high flame retardancy based on the US UL standards is required, and various flame retardant compositions have been proposed.
特開昭６１−１８８４５６号には、ナイロン４．６と臭
素化ポリスチレン又は臭素化ポリフェニレンエーテルと
からなる難燃性組成物が提案されている。しかしながら
かかる組成物は耐衝撃性が低く又成形品のウェルド部分
の強度が低いという欠点を有している。JP-A-61-188456 proposes a flame retardant composition comprising nylon 4.6 and brominated polystyrene or brominated polyphenylene ether. However, such compositions have the drawbacks of low impact resistance and low strength of the welded part of the molded article.
又特開昭５９−３０８５７号にはポリアミドとハロゲン
化ビスフェノール−Ａエポキシ樹脂からなる組成物が開
示されており、実施例ではナイロン６．６に添加した例
が示されているが、耐衝撃が低い。Furthermore, JP-A No. 59-30857 discloses a composition consisting of polyamide and halogenated bisphenol-A epoxy resin, and an example in which it is added to nylon 6.6 is shown, but the impact resistance is low.
我々はナイロン６．６、ナイロン６にブロム化ビスフェ
ノール−Ａエポキシ樹脂からなる組成物について検討し
たが、耐衝撃性が低いウェルド部の強度が低い又成形品
外観が劣った。We have investigated nylon 6.6, a composition consisting of nylon 6 and brominated bisphenol-A epoxy resin, but the impact resistance was low, the strength of the weld part was low, and the appearance of the molded product was poor.
Ｃ発明が解決しようとする問題点
以上の状況に鑑み本発明者等は、耐衝撃性、成形品外観
及びウェルド強度の改良されたポリアミド系難燃性組成
物について鋭意検討した。C Problems to be Solved by the Invention In view of the above circumstances, the present inventors have conducted extensive studies on polyamide flame retardant compositions with improved impact resistance, molded product appearance, and weld strength.
ｄ問題を解決するための手段
本発明は、ナイロン４．６にハロゲン化ビスフェノール
化合物を混合してなる難燃性ポリアミド組成物を提供す
るものである。d Means for Solving the Problem The present invention provides a flame-retardant polyamide composition comprising nylon 4.6 mixed with a halogenated bisphenol compound.
本発明に用いるナイロン４．６とは、実質的に←ＮＨ（
ＣＨｚ）＊ ＮＨＣｏ （ＣＨｚ）ａ−ＣＯ→の繰
返し構造単位によって構成されるポリアミドである。Nylon 4.6 used in the present invention is substantially ←NH(
CHz)*NHCo (CHz)A polyamide composed of repeating structural units of a-CO→.
このポリアミドの製造法については特開昭５６−１４９
４３号、特開昭５６−１４９４３号、特開昭５８−８３
０号及び特公昭６０−２８８号等に述べられている方法
を挙げることができる。Regarding the manufacturing method of this polyamide, Japanese Patent Application Laid-Open No. 56-149
No. 43, JP-A-56-14943, JP-A-58-83
Examples include methods described in Japanese Patent Publication No. 0 and Japanese Patent Publication No. 60-288.
また本発明による樹脂組成物を得るためには好ましくは
、１．５以上、更に好ましくは２．５〜５．０の相対粘
度（η、。、； ９７％硫酸１００ ｍｌ中ボリヌー
１ｇの溶液で３０゛Ｃで測定した。）を有するポリマー
を使用するのが有利である。In addition, in order to obtain the resin composition according to the present invention, the relative viscosity (η,.) is preferably 1.5 or more, more preferably 2.5 to 5.0; Advantageously, polymers with a temperature of 30° C.) are used.
本発明で使用されるハロゲン化ビスフェノール系化合物
は、一般式（Ｉ）で表わされるくり返し単位を有するも
のである。The halogenated bisphenol compound used in the present invention has a repeating unit represented by general formula (I).
Ｃ１ｈ ＯＨ
ハロゲン化ビスフェノール系化合物の更に好ましい化合
物は、一般式（ＩＩ）で表わされるものである。C1h OH A more preferable halogenated bisphenol compound is one represented by general formula (II).
ＣＩ（３
ハロゲン含量は２０％以上、好適には２５％以上である
。CI(3) The halogen content is at least 20%, preferably at least 25%.
特に有用なものはＸが臭素、ａ、、ｂ、Ｃ及ｄが２つで
あり、ｎが１２、以上である。Particularly useful are those in which X is bromine, a, b, C and d are two, and n is 12 or more.
特に好適のものは分子量が１５，０００以上のものであ
り、またｍ＝ｏのものである。Particularly preferred are those having a molecular weight of 15,000 or more, and those in which m=o.
またＲ、 、Ｒ，のうち少なくとも一方がであるものが
好ましく、特に好ましくは両方かのものである。Further, it is preferable that at least one of R, , and R is, and particularly preferably both of them are.
本発明に使用するハロゲン化ビスフェノール系化合物の
添加量は３〜４０重量％が好ましく、更に好ましくは５
〜３０重量％、特に好ましくは７〜２５重量％である。The amount of the halogenated bisphenol compound used in the present invention is preferably 3 to 40% by weight, more preferably 5% by weight.
-30% by weight, particularly preferably 7-25% by weight.
更に難燃助剤として例えば金属酸化物である５ｂ２０３
、ＺｎＯ−、Ｆｅ２Ｏ３等を使用した場合、好ましい
難燃効果を得ることができる。Furthermore, as a flame retardant aid, for example, 5b203 which is a metal oxide
, ZnO-, Fe2O3, etc., a preferable flame retardant effect can be obtained.
これら金属酸化物の使用量は、本発明の組成物中１〜２
０重量％が好ましく更に好ましくは２〜１５重量％であ
る。The amount of these metal oxides used is 1 to 2 in the composition of the present invention.
It is preferably 0% by weight, more preferably 2 to 15% by weight.
本発明の組成物には、上記一般式（ｎ）以外の含ハロゲ
ン難燃剤、例えばハロゲン化ビスフェノールエーテル、
ハロゲン化ポリスチレン、ハロゲン化ポリフヱニレンエ
ーテル等、リン系難燃剤、等を組合せて使用することが
できる。The composition of the present invention includes halogen-containing flame retardants other than the above general formula (n), such as halogenated bisphenol ether,
Halogenated polystyrene, halogenated polyphenylene ether, phosphorus flame retardants, etc. can be used in combination.
又一般にポリアミドに添加される添加剤を添加しても良
く、具体例としてガラス繊維、タルク、カオリン、チタ
ン酸カリウィスカー、ウオラストナイト、マイカ、クレ
ー等の強化剤、銅化合物等の安定剤、滑剤、着色剤等が
ある。Additionally, additives that are generally added to polyamides may be added, and specific examples include reinforcing agents such as glass fiber, talc, kaolin, potassium titanate whiskers, wollastonite, mica, and clay, stabilizers such as copper compounds, There are lubricants, colorants, etc.
本発明の組成物は種々の用途に使用することができる。The composition of the present invention can be used in a variety of applications.
例えば自動車部品として外板、ホイルキャンプ、ドアミ
ラーなどの外装部品、エンジンルーム、内部品、燃料フ
ィルター、排気ダクト、プーリー、ギアー類、ベアリン
グ部品、ケース類、オイルパンなどの機構部品、コネク
ターやランプケースなどの電装品などに使用でき、電気
・電子分野ではスイッチ、コネクター、フリント基板、
コイルボビン、ハウジングケース、ヒユーズケースなど
に使用でき、
機構部品分野では、ベアリング、ギヤー、軸受リベット
、ナンドなど、
また日用雑貨品、塗料、絶縁剤などに使用することがで
きる。For example, automotive parts include exterior parts such as outer panels, foil campsites, door mirrors, engine compartments, internal parts, fuel filters, exhaust ducts, pulleys, gears, bearing parts, cases, mechanical parts such as oil pans, connectors and lamp cases. It can be used for electrical components such as switches, connectors, flint boards, etc. in the electrical and electronic fields.
It can be used for coil bobbins, housing cases, fuse cases, etc. In the mechanical parts field, it can be used for bearings, gears, bearing rivets, NANDs, etc., as well as daily necessities, paints, insulation materials, etc.
次に実施例を挙げて本発明を更に詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例、比較例での評価方法を以下に説明する。Evaluation methods in Examples and Comparative Examples will be explained below.
１）燃焼時間
ＵＬ−９４に準じ燃焼試験を行ない燃焼時間を測定した
。1) Burning time A combustion test was conducted according to UL-94, and the burning time was measured.
２）成形品外観
燃焼試験片を射出成形し、成形品表面の肌荒れ、気泡、
色等を見た。以下の評価基準に従って見視評価した。2) Molded product appearance combustion test piece was injection molded, and the surface of the molded product was rough, bubbles,
I looked at the colors etc. Visual evaluation was performed according to the following evaluation criteria.
○；良好 ×；悪い
３）耐衝撃性
ＡＳＴＭ Ｄ２５６に従ってノツチ付２３℃でアイゾ
ツト衝撃強度を測定した。○: Good ×: Bad 3) Impact resistance Izot impact strength was measured at 23° C. with a notch according to ASTM D256.
４）ウェルド強度
ウェルド部を有する成形品を成形し、折り曲げて強度を
見た。評価は以下の基準に従って行なった。4) Weld strength A molded product having a welded part was molded and bent to examine its strength. Evaluation was performed according to the following criteria.
○；強い
×；弱い
実施例１〜４、比較例１〜４
表−１の組成割合に従って混合し、二軸押出機を用いて
ペレット化した。充分乾燥した後、射出成形機を用い各
種成形品を得た後、前記評価法に従って評価した。○: Strong ×: Weak Examples 1 to 4, Comparative Examples 1 to 4 They were mixed according to the composition ratios in Table 1, and pelletized using a twin-screw extruder. After sufficient drying, various molded products were obtained using an injection molding machine, and then evaluated according to the evaluation method described above.
評価結果を表−１に示した。The evaluation results are shown in Table-1.
難燃剤種として以下のものを用いた。The following flame retardants were used.
臭素化ビスフェノールＡエポキシ樹脂
；ＭＡＫＨＴＥＳＨＩＭ社製Ｆ２４００大日本インキ化
学社製ＰＲＡＴＨＥＲＭＦＲ５００
臭素化ポリスチレン
、ＦＥＲＲＯ社製Ｐｙｒｏ−Ｃｈｅｋ６８Ｐ臭素化ポリ
フェニレンエーテル
ＨＧｒｅａｔ Ｌａｋｅｓ社製ＰＯ−６４Ｐ使用した
ナイロン
ナイロン４．６；η、、、３．５を使用した。Brominated bisphenol A epoxy resin; MAKHTESHIM F2400 Dainippon Ink Chemical Co. PRATHERMFR500 Brominated polystyrene, FERRO Pyro-Chek68P Brominated polyphenylene ether HGreat Lakes PO-64P Nylon 4.6; η, , 3.5 was used.
ナイロン６．６；東し製アミラン”ＣＭ３００６を使用
した。Nylon 6.6: Amiran CM3006 manufactured by Toshi was used.
発明の効果
本発明の組成物は高度な難燃性を有し、優れた耐衝撃性
、成形品外観及びウェルド強度を有する。Effects of the Invention The composition of the present invention has high flame retardancy, excellent impact resistance, molded product appearance, and weld strength.
Claims (3)
単位を有するハロゲン化ビスフェノール系化合物を混合
してなる難燃性ポリアミド組成物。 （ I ）▲数式、化学式、表等があります▼ ［式中Ｘは臭素および塩素から選ばれた少なくとも１種
、ａおよびｂは０〜４の整数、但しａ＋ｂは２以上、 Ｒは炭素数１〜６のアルテレン残基、ｎは自然数である
。］(1) A flame-retardant polyamide composition prepared by mixing nylon 4 and 6 with a halogenated bisphenol compound having a repeating unit represented by formula (I). (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, ~6 alterene residues, n being a natural number. ]
あり、Ｒがプロピレン残基であり、かつ分子末端の少な
くとも一方にエポキシ基を有するものである特許請求の
範囲第（１）項記載の難燃性ポリアミド組成物。(2) The problem described in claim (1), wherein the halogenated bisphenol compound is one in which n≧5, R is a propylene residue, and has an epoxy group at at least one of the molecular terminals. Flammable polyamide composition.
４０重量％である特許請求の範囲第（１）項記載の難燃
性ポリアミド組成物。(3) Content of halogenated bisphenol compound is 3~
40% by weight of the flame retardant polyamide composition according to claim (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26493186A JPS63118368A (en) | 1986-11-07 | 1986-11-07 | Flame-retardant polyamide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26493186A JPS63118368A (en) | 1986-11-07 | 1986-11-07 | Flame-retardant polyamide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63118368A true JPS63118368A (en) | 1988-05-23 |
Family
ID=17410178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26493186A Pending JPS63118368A (en) | 1986-11-07 | 1986-11-07 | Flame-retardant polyamide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63118368A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006123715A1 (en) * | 2005-05-20 | 2006-11-23 | Nitto Shinko Corporation | Multilayer sheet |
-
1986
- 1986-11-07 JP JP26493186A patent/JPS63118368A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006123715A1 (en) * | 2005-05-20 | 2006-11-23 | Nitto Shinko Corporation | Multilayer sheet |
| JP2006321183A (en) * | 2005-05-20 | 2006-11-30 | Nitto Shinko Kk | Laminate sheet |
| US7713892B2 (en) | 2005-05-20 | 2010-05-11 | Nitto Shinko Corporation | Laminate sheet |
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