JPH0665706B2 - Flame-retardant nylon 4-6 composition - Google Patents
Flame-retardant nylon 4-6 compositionInfo
- Publication number
- JPH0665706B2 JPH0665706B2 JP60027991A JP2799185A JPH0665706B2 JP H0665706 B2 JPH0665706 B2 JP H0665706B2 JP 60027991 A JP60027991 A JP 60027991A JP 2799185 A JP2799185 A JP 2799185A JP H0665706 B2 JPH0665706 B2 JP H0665706B2
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- composition
- flame
- brominated
- polyphenylene ether
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、難燃性ナイロン４−６組成物に関する。TECHNICAL FIELD The present invention relates to a flame-retardant nylon 4-6 composition.
本発明組成物は、電気・電子分野の部品、特にコネクタ
ーやコイルボビンの用途に好適である。The composition of the present invention is suitable for use in parts in the electric and electronic fields, particularly connectors and coil bobbins.
［従来の技術］ 電気・電子分野においては、米国のUL規格に基づく高い
難燃性が要求され、これに対し種々のハロゲン系難燃性
が提案されてきた。特にハロゲン系難燃性のブルーム性
を改良した優れたものとして、特開昭57−53505（臭素
化ポリスチレンの製法）、特開昭51−47044（ポリアミ
ドと臭素化ポリスチレンとからなる組成物）、特開昭54
−116054（ナイロンと臭素化ポリフェニレンエーテルと
からなる組成物）が提案されたが、いずれも成形品外観
が良好でなかった。[Prior Art] In the electric and electronic fields, high flame retardancy based on the UL standard of the United States is required, and various halogen-based flame retardancy has been proposed for this. In particular, as an excellent one having improved halogen-based flame retardant blooming property, JP-A-57-53505 (manufacturing method of brominated polystyrene), JP-A-51-47044 (composition composed of polyamide and brominated polystyrene), JP-A-54
-116054 (composition composed of nylon and brominated polyphenylene ether) was proposed, but none of them had a good appearance of the molded article.
［本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らは、高度な難燃性を有し、
ブルーミングがなくかつ良好な成形品外観を有する難燃
性組成物を得るべく鋭意検討した。[Problems to be Solved by the Present Invention] In view of the above situation, the present inventors have high flame retardancy,
The inventors have made earnest studies to obtain a flame-retardant composition having no blooming and a good appearance of a molded article.
［問題点を解決するための手段及び作用］ その結果、ナイロン４−６と式（ａ）に示すくり返し単
位を有する臭素化ポリスチレンは式（ｂ）に示す臭素化
ポリフェニレンエーテルとの組成物がすべての問題を解
決できることを見出し本発明に到った。[Means and Actions for Solving Problems] As a result, the composition of nylon 4-6 and the brominated polystyrene having the repeating unit represented by the formula (a) is the same as that of the brominated polyphenylene ether represented by the formula (b). The inventors of the present invention have found that the above problems can be solved and have reached the present invention.
本発明でいうナイロン４−６とは、テトラメチレンジア
ミンとアジピン酸を重合して得られらる線状高分子量ポ
リアミドであり、その製法は、例えばテトラメチレンジ
アミンとアジピン酸とを水溶液中150〜310℃で加熱し、
プレポリマーを作り、これを更に融点以上の温度で固相
重合する方法がとられる。Nylon 4-6 in the present invention is a linear high molecular weight polyamide obtained by polymerizing tetramethylenediamine and adipic acid, and the production method thereof is, for example, tetramethylenediamine and adipic acid in an aqueous solution of 150- Heated at 310 ° C,
A method of preparing a prepolymer and further solid-phase polymerizing the prepolymer at a temperature equal to or higher than the melting point is used.
本発明でいう臭素化ポリスチレンは次式で示されるくり
返し単位を有する。The brominated polystyrene referred to in the present invention has a repeating unit represented by the following formula.
（ｎは整数。１≦ｎ≦５） 該臭素化ポリスチレンの臭素含有量は65〜75重量％のも
のが好ましい。ｎで言えば約３のものが好ましい。 (N is an integer. 1≤n≤5) The brominated polystyrene preferably has a bromine content of 65 to 75% by weight. Speaking of n, about 3 is preferable.
該臭素化ポリスチレンの製法は特に限定されないが、ポ
リスチレンの該臭素化反応によって製造することができ
る。The method for producing the brominated polystyrene is not particularly limited, but it can be produced by the bromination reaction of polystyrene.
本発明でいう臭素化ポリフェニレンエーテルは次式で表
わされる。The brominated polyphenylene ether referred to in the present invention is represented by the following formula.
（ｍは５〜200の整数） 臭素化ポリスチレンヌは臭素化ポリフェニレンエーテル
の添加量は５〜30重量％が好ましい。 (M is an integer of 5 to 200) In brominated polystyrene, the amount of brominated polyphenylene ether added is preferably 5 to 30% by weight.
難燃助剤を添加することは好ましい。例えば金属酸化物
Sb2O3,ZnO,Fe2O3等である。It is preferable to add a flame retardant aid. For example metal oxide
Sb 2 O 3 , ZnO, Fe 2 O 3 and the like.
また、一般にポリアミドに添加される添加剤は添加して
も差支えない。強化剤としてガラス繊維、タルク、カオ
リン、ウォラストナイト、マイカ等の無機フィラー、銅
化合物等の安定剤、滑剤、着色剤等添加し得る。In addition, it does not matter if an additive that is generally added to polyamide is added. As a reinforcing agent, glass fiber, talc, kaolin, wollastonite, inorganic filler such as mica, stabilizer such as copper compound, lubricant, coloring agent and the like may be added.
［実施例］ 次に実施例を挙げて本発明を説明する。EXAMPLES Next, the present invention will be described with reference to examples.
実施例、比較例での評価方法を次に示す。The evaluation methods in Examples and Comparative Examples are shown 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 burning test was performed according to UL-94 to measure the burning time.
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、
色の３点の総合評価で、この３点を下記測定方法及び基
準に基づいて評価した結果得られた最も悪い評価を総合
評価としての成形品外観の評価として下記記号で示し
た。2) Appearance of molded product Combustion test pieces are injection molded, and the surface of the molded product is roughened, air bubbles,
In the overall evaluation of the three points of color, the worst evaluation obtained as a result of evaluating these three points based on the following measuring methods and criteria is shown by the following symbols as the evaluation of the appearance of the molded article as the overall evaluation.
○……問題なし。○ …… No problem.
△……やや悪い。△ …… Slightly bad.
×……割い。× …… Allow.
肌荒れ、気泡、色の評価基準は次の通りである。The evaluation criteria for rough skin, bubbles, and color are as follows.
肌荒れ：成形品の表面をグロスメーターで測定し、下
記基準に基づいて評価した。尚、表２に下記記号と共に
記載したかっこ内の値はグロスメーターの測定値であ
る。Rough skin: The surface of the molded product was measured with a gloss meter and evaluated based on the following criteria. The values in parentheses shown in Table 2 together with the following symbols are the values measured by a gloss meter.
50以上………………○ 20以上50未満……△ 20未満………………× 気泡：気泡の発生の有無を目視にて評価した。50 or more ……………… ○ 20 or more but less than 50 …… △ less than 20 ……………… Bubbles: The presence or absence of bubbles was visually evaluated.
気泡の発生が認められないもの……○（なし） 気泡の発生率３％以下のもの………○（ほとんどなし） 気泡の発生率３〜10％のもの……△（少し） 色：実施例で得た成形品と、実施例のナイロン４−６
に変えてナイロン66を用いた場合の成形品の色差（Δ
Ｅ）を色差計を用いて測定した。尚、表２に下記記号と
共に記載したかっこ内の値は測定したΔＥの値である。No air bubble formation …… ○ (none) Air bubble generation rate of 3% or less ………… ○ (almost none) Air bubble generation rate of 3-10% …… △ (little) Color: Implemented The molded product obtained in the example and nylon 4-6 in the example
Color difference (Δ) of the molded product when nylon 66 is used instead of
E) was measured using a color difference meter. The values in parentheses shown in Table 2 together with the following symbols are the measured ΔE values.
ΔＥ＜５ ……○ ３）ブルーミング性 燃焼試験片を熱風オーブン中で140℃で３日間エージン
グし、表面状態を観察した。ΔE <5 ... ○ 3) Blooming property The combustion test piece was aged in a hot air oven at 140 ° C for 3 days, and the surface condition was observed.
結果は次の記号で表現した。The results are expressed by the following symbols.
○……表面は汚れていない。○: The surface is not dirty.
×……表面が著しく汚れている。×: The surface is extremely dirty.
実施例１ ナイロン４−６に臭素化ポリスチレンを15wt％添加し燃
焼時間、成形品外観、ブルーミング性を評価した。結果
を表１に示す。Example 1 15 wt% of brominated polystyrene was added to nylon 4-6, and the burning time, appearance of molded articles and blooming properties were evaluated. The results are shown in Table 1.
実施例２、比較例１〜４ ナイロン４−６に臭素化ポリフェニレンエーテル15wt％
（実施例２）、ナイロン４−６にデカブロモジフェニル
エーテル15wt％（比較例１）、ナイロン66に臭素化ポリ
スチレン15wt％（比較例２）を添加したもの、ナイロン
４−６そのもの（比較例３）及びナイロン66に臭素化ポ
リフェニレンエーテル15wt％（比較例４）を添加したも
のについて燃焼時間、成形品外観、ブルーミング性を評
価した。結果を表１に示す。また、成形品外観評価の詳
細を表２に示す。Example 2, Comparative Examples 1-4 Nylon 4-6 with brominated polyphenylene ether 15 wt%
(Example 2), Nylon 4-6 with 15 wt% decabromodiphenyl ether (Comparative Example 1), Nylon 66 with 15 wt% brominated polystyrene (Comparative Example 2), nylon 4-6 itself (Comparative Example 3) Also, a composition obtained by adding brominated polyphenylene ether 15 wt% (Comparative Example 4) to nylon 66 was evaluated for the burning time, the appearance of the molded product, and the blooming property. The results are shown in Table 1. Table 2 shows the details of the appearance evaluation of the molded product.
但し、臭素化ポリスチレンとしてはフェロ社製パイロチ
ェック68PBを、臭素化ポリフェニレンエーテルとしては
グレートレイクス社製PO 64Pを用いた。However, Pyrocheck 68PB manufactured by Ferro was used as the brominated polystyrene, and PO 64P manufactured by Great Lakes was used as the brominated polyphenylene ether.
［発明の効果］ 本発明の組成物は高度な難燃性を有し、優れた成形品外
観を有し、ブルーミングがない。 [Effect of the Invention] The composition of the present invention has a high degree of flame retardancy, has an excellent molded article appearance, and is free from blooming.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 25:18） (Ｃ０８Ｌ 77/06 71:12） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display area C08L 25:18) (C08L 77/06 71:12)
Claims (2)
単位を有する臭素化ポリスチレン又は式（ｂ）で示す臭
素化ポリフェニレンエーテルとの難燃性組成物。 （ｍは５〜200の整数）1. A flame-retardant composition of nylon 4-6 and brominated polystyrene having a repeating unit represented by formula (a) or brominated polyphenylene ether represented by formula (b). (M is an integer from 5 to 200)
単位を有する臭素化ポリスチレン又は式（ｂ）で示す臭
素化ポリフェニレンエーテルとの難燃性組成物よりなる
コネクター又はボビン。 （ｍは５〜200の整数）2. A connector or bobbin comprising a flame-retardant composition of nylon 4-6 and brominated polystyrene having a repeating unit represented by formula (a) or brominated polyphenylene ether represented by formula (b). (M is an integer from 5 to 200)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60027991A JPH0665706B2 (en) | 1985-02-15 | 1985-02-15 | Flame-retardant nylon 4-6 composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60027991A JPH0665706B2 (en) | 1985-02-15 | 1985-02-15 | Flame-retardant nylon 4-6 composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61188463A JPS61188463A (en) | 1986-08-22 |
| JPH0665706B2 true JPH0665706B2 (en) | 1994-08-24 |
Family
ID=12236289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60027991A Expired - Lifetime JPH0665706B2 (en) | 1985-02-15 | 1985-02-15 | Flame-retardant nylon 4-6 composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0665706B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7718756B2 (en) | 2006-08-22 | 2010-05-18 | Chemtura Corporation | Brominated flame retardant |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0689251B2 (en) * | 1986-02-28 | 1994-11-09 | 日本合成ゴム株式会社 | Flame-retardant resin composition |
| JPH0761659B2 (en) * | 1986-10-22 | 1995-07-05 | 旭化成工業株式会社 | Flame-retardant polyamide moldings |
| JP2808106B2 (en) * | 1986-12-02 | 1998-10-08 | ジェイエスアール株式会社 | Nylon resin composition |
| CA1338392C (en) * | 1987-04-20 | 1996-06-11 | Mitsui Chemicals, Incorporated | Fire-retardant polyamide composition having good heat resistance |
| JPH01174561A (en) * | 1987-12-28 | 1989-07-11 | Toyobo Co Ltd | Thermoplastic resin composition |
| JP2582878B2 (en) * | 1988-11-22 | 1997-02-19 | 東レ株式会社 | Flame retardant polyamide resin composition |
| JPH08208980A (en) * | 1995-11-10 | 1996-08-13 | Japan Synthetic Rubber Co Ltd | Flame-retardant resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5147044A (en) * | 1974-10-22 | 1976-04-22 | Teijin Ltd | NANNENSEI HORIAMIDOSOSEIBUTSU |
| US4141880A (en) * | 1978-01-03 | 1979-02-27 | Velsicol Chemical Corporation | Flame retarded nylon composition |
| DE2923121A1 (en) * | 1979-06-07 | 1980-12-18 | Siemens Ag | METHOD AND CIRCUIT ARRANGEMENT FOR CARRYING OUT A PLAUSIBILITY CHECK WITH REGARD TO FOLLOWING TIME INFORMATION IN TRAFFIC SIGNAL SYSTEMS |
| NL8001762A (en) * | 1980-03-26 | 1981-10-16 | Stamicarbon | PREPARATION OF ARTICLES BASED ON POLYAMIDE. |
| US4352909A (en) * | 1980-08-20 | 1982-10-05 | Ferro Corporation | Process for the bromination of polystyrenes |
| US4373049A (en) * | 1981-11-05 | 1983-02-08 | E. I. Du Pont De Nemours And Company | Flame-retardant polyamide compositions |
-
1985
- 1985-02-15 JP JP60027991A patent/JPH0665706B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7718756B2 (en) | 2006-08-22 | 2010-05-18 | Chemtura Corporation | Brominated flame retardant |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61188463A (en) | 1986-08-22 |
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