JPS63118368A - Flame-retardant polyamide composition - Google Patents

Flame-retardant polyamide composition

Info

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
Application number
JP26493186A
Other languages
Japanese (ja)
Inventor
Masaaki Motai
政明 馬渡
Junji Kamishina
順二 神品
Hideji Tsuchikawa
土川 秀治
Shinichi Kimura
木村 慎一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JSR Corp
Original Assignee
Japan Synthetic Rubber Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Japan Synthetic Rubber Co Ltd filed Critical Japan Synthetic Rubber Co Ltd
Priority to JP26493186A priority Critical patent/JPS63118368A/en
Publication of JPS63118368A publication Critical patent/JPS63118368A/en
Pending legal-status Critical Current

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Abstract

PURPOSE:To obtain the titled composition, having improved impact resistance, external appearance as well as weld strength of molded articles and suitable as automotive parts, mechanical parts, etc., by blending nylon 4, 6 with a specific halogenated bisphenol based compound. CONSTITUTION:A composition obtained by blending nylon 4, 6 consisting of repeating units expressed by formula I with 3-40wt%, preferably 7-25wt% halogenated bisphenol based compound, having repeating units expressed by formula II (X is bromine, etc.; a and b are 0-4 and a+b is >=2; R is 1-6C alkylene residue; n is a natural number, preferably n is >=5; R is propylene residue) and epoxy group in at least one of the molecular terminals.

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.

〔実施例〕〔Example〕

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)

【特許請求の範囲】[Claims] (1)ナイロン4、6に式( I )で示されるくり返し
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. ]
(2)ハロゲン化ビスフェノール系化合物が、n≧5で
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.
(3)ハロゲン化ビスフェノール化合物の含有量が3〜
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).
JP26493186A 1986-11-07 1986-11-07 Flame-retardant polyamide composition Pending JPS63118368A (en)

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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006123715A1 (en) * 2005-05-20 2006-11-23 Nitto Shinko Corporation Multilayer sheet

Cited By (3)

* Cited by examiner, † Cited by third party
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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