JPS63308062A - Flame-retardant polyamide polymer composition - Google Patents
Flame-retardant polyamide polymer compositionInfo
- Publication number
- JPS63308062A JPS63308062A JP14479787A JP14479787A JPS63308062A JP S63308062 A JPS63308062 A JP S63308062A JP 14479787 A JP14479787 A JP 14479787A JP 14479787 A JP14479787 A JP 14479787A JP S63308062 A JPS63308062 A JP S63308062A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- flame
- parts
- weight
- flame retardant
- 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
- 239000004952 Polyamide Substances 0.000 title claims abstract description 19
- 229920002647 polyamide Polymers 0.000 title claims abstract description 19
- 239000003063 flame retardant Substances 0.000 title claims abstract description 14
- 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 abstract description 12
- 239000000203 mixture Substances 0.000 title abstract description 5
- 229920000642 polymer Polymers 0.000 title 1
- 229920001971 elastomer Polymers 0.000 claims abstract description 20
- 239000000806 elastomer Substances 0.000 claims abstract description 11
- -1 polyoxymethylene Polymers 0.000 claims abstract description 10
- 239000005060 rubber Substances 0.000 claims abstract description 9
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 5
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 5
- 229920006122 polyamide resin Polymers 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 4
- 150000002367 halogens Chemical class 0.000 abstract description 4
- 229920001973 fluoroelastomer Polymers 0.000 abstract description 2
- 229920001084 poly(chloroprene) Polymers 0.000 abstract description 2
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000299 Nylon 12 Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- ZIWYFFIJXBGVMZ-UHFFFAOYSA-N dioxotin hydrate Chemical compound O.O=[Sn]=O ZIWYFFIJXBGVMZ-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000012796 inorganic flame retardant Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NLJYVSRAICBDSH-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,15-triacontachlorocyclopentadecane Chemical compound ClC1(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C1(Cl)Cl NLJYVSRAICBDSH-UHFFFAOYSA-N 0.000 description 1
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は難燃性ポリアミド樹脂組成物に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to flame retardant polyamide resin compositions.
ざらに詳しくは、柔軟性及び難燃性に勝れたポリアミド
樹脂組成物に関する。More specifically, the present invention relates to a polyamide resin composition with excellent flexibility and flame retardancy.
（従来技術および問題点）
ポリアミド樹脂は耐油性、耐溶剤性、耐熱性、靭性等に
優れるため、チューブ、ホース、？ｌｉｌ波線、電気部
品、自動車部品等として広く用いられている。とりわけ
ポリアミド樹脂に可塑剤を添加し、柔軟性を付与したポ
リアミド樹脂組成物は、自動車用チューブ、各種油圧機
器、空圧機器、作動用チューブ、ホースとして好適に使
用されている。(Prior art and problems) Polyamide resin has excellent oil resistance, solvent resistance, heat resistance, toughness, etc., so it can be used for tubes, hoses, etc. It is widely used as lil wavy wire, electrical parts, automobile parts, etc. In particular, polyamide resin compositions obtained by adding a plasticizer to polyamide resin to impart flexibility are suitably used as tubes for automobiles, various hydraulic equipment, pneumatic equipment, operating tubes, and hoses.
しかし、これらチューブ、ホースが例えば溶接用ロボッ
トのように複雑な動作を行ない、燃焼の恐れが極めて高
い環境で使用される場合、可どう性、難燃性等の点にお
いて十分満足して使用できるものではない。However, when these tubes and hoses perform complex operations, such as in welding robots, and are used in environments where the risk of combustion is extremely high, they can be used satisfactorily in terms of flexibility, flame retardance, etc. It's not a thing.
ポリアミド樹脂は本来自己消火性を有しているが、柔軟
性を付与するため、可塑剤等の易揮発性を有する化合物
を多産に添加すると、著しく難燃性が損われる。また、
高度な可どう性を付与するために可塑剤の添加量を増大
させると、難燃性を損うばかりでなく、可塑剤のブリー
ドアウト、揮散等を起すため、実質的に可塑剤の添加量
には限界があり、十分な柔軟性を付与することは困難で
ある。Polyamide resins inherently have self-extinguishing properties, but if readily volatile compounds such as plasticizers are frequently added to impart flexibility, flame retardancy is significantly impaired. Also,
Increasing the amount of plasticizer added to impart a high degree of plasticity not only impairs flame retardancy, but also causes bleed-out and volatilization of the plasticizer, so the amount of plasticizer added actually increases. There are limits to this, and it is difficult to provide sufficient flexibility.
本発明者はかかる問題点を解決するために検討を行なっ
た結果、特定のポリアミドエラストマーにハロゲン化ゴ
ム及び難燃剤をＭｙｉ配合することにより、柔軟かつ難
燃性に勝れたポリアミド樹脂組成物の得られることを見
出し、この知見に基づいて本発明をなすに至った。The present inventor conducted studies to solve these problems, and found that by blending halogenated rubber and a flame retardant into a specific polyamide elastomer, a polyamide resin composition with excellent flexibility and flame retardancy was created. The present invention has been completed based on this finding.
（問題点を解決するための手段）
すなわち本発明は、ハードセグメントをポリアミド、ソ
フトセグメントをポリオキシメチレンとするポリアミド
エラストマー共重合体１００重量部に対して、ハロゲン
化ゴムを３０〜１００ｍ１部、難燃剤を３０〜８０重量
部配合してなる柔軟かつ難燃性にうれたポリアミド樹脂
組成物である。(Means for Solving the Problems) That is, the present invention provides 1 part by weight of halogenated rubber of 30 to 100 ml per 100 parts by weight of a polyamide elastomer copolymer in which the hard segment is polyamide and the soft segment is polyoxymethylene. This is a flexible and flame-retardant polyamide resin composition containing 30 to 80 parts by weight of a flame agent.
本発明に用いるポリアミドエラストマー共重合体のハー
ドセグメントとしてのポリアミドには、ナイロン６、ナ
イロン１１、ナイロン１２、ナイロン６６、ナイロン６
１０、ナイロン６１２等が例示できるが、好ましくはナ
イロン１１、ナイロン１２である。ソフトセグメントと
してのポリオキシメチレンには、ポリオキシテトラメチ
レングリコールや次式に示す様なポリオキシテトラメチ
レンのジアミンなどがあげられる。ソフトセグメントの
数平均分子口は１６０〜３０００である。Polyamides used as hard segments of the polyamide elastomer copolymer used in the present invention include nylon 6, nylon 11, nylon 12, nylon 66, and nylon 6.
Examples include nylon 10 and nylon 612, but nylon 11 and nylon 12 are preferable. Examples of polyoxymethylene as a soft segment include polyoxytetramethylene glycol and polyoxytetramethylene diamine as shown in the following formula. The number average molecular weight of the soft segment is 160-3000.
１１１Ｎ（ＣＨ工）３０［（ＣＨよ）参０１２（Ｃｔｌ
ｚ）３Ｎ＋１．Ｌポリアミドエラストマー共重合体のポ
リアミド成分は３０〜９５重量部、ポリオキシメチレン
成分は５〜７０重量部である。具体的なものとしては特
公昭５６−４５４１９、特開昭５５−１３３４２４に例
示されるポリアミドエラストマーがある。111N (CH engineering) 30 [(CHyo) 012 (Ctl
z)3N+1. The polyamide component of the L polyamide elastomer copolymer is 30 to 95 parts by weight, and the polyoxymethylene component is 5 to 70 parts by weight. Specific examples include polyamide elastomers as exemplified in Japanese Patent Publication No. 56-45419 and Japanese Patent Application Laid-Open No. 55-133424.
本発明で使用するハロゲン化ゴムとしては、ハロゲン含
有率が３０％以上のクロロブレンゴム、りＯロスルホン
化ポリエチレン、塩素化ポリエチレン、フッ素ゴム等の
一種又は二種以上を混合して使用することができる。As the halogenated rubber used in the present invention, one or a mixture of two or more of chloroprene rubber having a halogen content of 30% or more, oxysulfonated polyethylene, chlorinated polyethylene, fluororubber, etc. can be used. can.
これらハロゲン化ゴムの配合量は、ポリアミドエラスト
マー１００重量部に対して３０〜１００重量部、好まし
くは３０〜８０重資部であり、３０重量部より少ないと
燃焼時にドリッピングを生じる。１００重廼都合越えて
添加することは機械強度、耐薬品性を著しく低下させる
ばかりでなく、加工時に着色を生じ好ましくない。The blending amount of these halogenated rubbers is 30 to 100 parts by weight, preferably 30 to 80 parts by weight, per 100 parts by weight of the polyamide elastomer, and if it is less than 30 parts by weight, dripping occurs during combustion. Adding more than 100% of the total weight not only significantly lowers mechanical strength and chemical resistance but also causes discoloration during processing, which is undesirable.
本発明で使用する難燃剤としては、トリクレジルホスフ
ェート、クレジルフェニルホスフェート、オクチルフェ
ニルホスフェート等に代表されるリン酸エステル系、ト
リス（２，３−ブロモプロピル）ホスフェート、トリス
（ブロモクロロプロピル）ホスフェートに代表されるハ
ロゲン化リン酸エステル系、芳香族ポリホスフェート、
デカブロモジフェニルエーテル、デカブロモビフェニル
、ヘキサブロムベンゼン、テトラブロモビスフェノール
Ａ１パークロロシクロペンタデカン等に代表される含ハ
ロゲン難燃剤、酸化アンチモン、メタホウ酸バリウム、
酸化スズ水和物、水酸化アルミニウム等の無機系難燃剤
のいずれを使用してもよく、これらの一種又は二種以上
を混合して使用することができる。好ましくは含ハロゲ
ン難燃剤と酸化アンチモン、酸化スズ水和物等の無機系
難燃剤を併用するのが良い。The flame retardants used in the present invention include phosphate esters such as tricresyl phosphate, cresyl phenyl phosphate, octylphenyl phosphate, tris(2,3-bromopropyl) phosphate, and tris(bromochloropropyl). Halogenated phosphate esters represented by phosphates, aromatic polyphosphates,
Halogen-containing flame retardants such as decabromodiphenyl ether, decabromo biphenyl, hexabromobenzene, tetrabromobisphenol A1 perchlorocyclopentadecane, antimony oxide, barium metaborate,
Any inorganic flame retardant such as tin oxide hydrate and aluminum hydroxide may be used, and one or more of these may be used in combination. Preferably, a halogen-containing flame retardant and an inorganic flame retardant such as antimony oxide or tin oxide hydrate are used in combination.
難燃剤の配合量は、ポリアミドエラストマー共重合体１
００重１部に対して３０〜８０１１部である。３０重量
部より少ないと難燃効果が不十分であり、８０重鎖部を
越えて添加すると柔軟性が損われたり、ブルーミングを
生じる恐れがある。The blending amount of the flame retardant is 1 part polyamide elastomer copolymer
The amount is 30 to 8011 parts per part of 00 weight. If it is less than 30 parts by weight, the flame retardant effect will be insufficient, and if it is added in excess of 80 parts by weight, flexibility may be impaired or blooming may occur.
これらポリアミドエラストマー共重合体、ハロゲン化ゴ
ム、難燃剤の混合混線は、通常一般に用いられる混線方
法でもって行うことができるが、好ましくは二軸押出機
を用いる方法が良い。The polyamide elastomer copolymer, halogenated rubber, and flame retardant can be mixed by a commonly used mixing method, but preferably a twin-screw extruder is used.
本発明のポリアミド組成物を混合混練するに当たり、必
要に応じて耐熱安定剤、耐候安定剤、着色料その他の助
剤を添加混練することは、回答本発明の効果を損うもの
ではない。When mixing and kneading the polyamide composition of the present invention, adding and kneading a heat-resistant stabilizer, a weather-resistant stabilizer, a coloring agent, and other auxiliary agents as necessary does not impair the effects of the present invention.
（発明の効果）
本発明により得られるポリアミド樹脂組成物は柔軟性、
難燃性に優れており、油圧、空圧チューブ、ホースさら
には電線被覆材料として広く用いることができる。(Effects of the invention) The polyamide resin composition obtained by the invention has flexibility,
It has excellent flame retardancy and can be widely used as a coating material for hydraulic and pneumatic tubes, hoses, and electric wires.
（実 施 例）
以下実施例によって本発明を説明するが、実施例によっ
て本発明の範囲が限定されるものではない。(Examples) The present invention will be explained below with reference to Examples, but the scope of the present invention is not limited by the Examples.
ポリアミドエラストマー共重合体に表１に示す配合割合
のハロゲン化ゴム及び難燃剤を配合し、中央１械製３０
ＨＩＩφ二軸押出機により混練して均一なベレットを得
た。得られたペレットから射出成形法により物性測定用
試験片を成形し、柔軟性、燃焼性を下記の試験法で評価
した。結果を表１に示す。A polyamide elastomer copolymer was blended with halogenated rubber and a flame retardant in the proportions shown in Table 1, and 30
A homogeneous pellet was obtained by kneading using an HIIφ twin-screw extruder. Test pieces for measuring physical properties were molded from the obtained pellets by injection molding, and flexibility and flammability were evaluated using the following test methods. The results are shown in Table 1.
燃焼性
ＵＬ規格９４Ｖ−０と認定するための試験法に準拠して
行なった。The test was conducted in accordance with the test method for certifying flammability as UL Standard 94V-0.
ドリップ ０ １０サンプルでドリップ Ｏ Δ １ × １以上 燃焼時間drip 0 Drip with 10 samples O Δ 1 × 1 or more Burning time
Claims (1)
リオキシメチレンとするポリアミドエラストマー共重合
体１００重量部に対して、ハロゲン化ゴムを３０〜１０
０重量部、難燃剤を３０〜８０重量部配合してなる柔軟
かつ難燃性に優れたポリアミド樹脂組成物。30 to 10 parts of halogenated rubber is added to 100 parts by weight of a polyamide elastomer copolymer in which the hard segment is polyamide and the soft segment is polyoxymethylene.
A polyamide resin composition having excellent flexibility and flame retardancy, which contains 0 parts by weight and 30 to 80 parts by weight of a flame retardant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14479787A JPS63308062A (en) | 1987-06-10 | 1987-06-10 | Flame-retardant polyamide polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14479787A JPS63308062A (en) | 1987-06-10 | 1987-06-10 | Flame-retardant polyamide polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63308062A true JPS63308062A (en) | 1988-12-15 |
Family
ID=15370682
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14479787A Pending JPS63308062A (en) | 1987-06-10 | 1987-06-10 | Flame-retardant polyamide polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63308062A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59193958A (en) * | 1983-04-18 | 1984-11-02 | Dainippon Ink & Chem Inc | Sealing material |
-
1987
- 1987-06-10 JP JP14479787A patent/JPS63308062A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59193958A (en) * | 1983-04-18 | 1984-11-02 | Dainippon Ink & Chem Inc | Sealing material |
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