JP2582392B2 - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JP2582392B2 JP2582392B2 JP63007837A JP783788A JP2582392B2 JP 2582392 B2 JP2582392 B2 JP 2582392B2 JP 63007837 A JP63007837 A JP 63007837A JP 783788 A JP783788 A JP 783788A JP 2582392 B2 JP2582392 B2 JP 2582392B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- alcohol
- resin composition
- acid
- plasticizer
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は柔軟性の優れたポリアミド樹脂組成物に関す
るものである。The present invention relates to a polyamide resin composition having excellent flexibility.
〔従来の技術及び発明が解決しようとする課題〕 ポリアミド樹脂はそれ自体ある程度の柔軟性を有して
いるが、チューブ、ホースなどの用途にはより大きな柔
軟性が要求される。[Problems to be Solved by Conventional Techniques and Inventions] Polyamide resins themselves have some flexibility, but applications such as tubes and hoses require greater flexibility.
この柔軟性を付与するために、ポリアミド樹脂に芳香
族スルホンアミド類、パラ−ヒドロキシ安息香酸２−エ
チルヘキシルなどの可塑剤を配合している。In order to impart this flexibility, a plasticizer such as aromatic sulfonamides and 2-ethylhexyl para-hydroxybenzoate is blended with the polyamide resin.
しかし、これらの可塑剤はポリアミド樹脂との相溶性
が十分でないので、成形物の表面に可塑剤が浸出し、べ
たつくという欠点があり、また成形物を高温で長時間使
用すると可塑剤が飛散し、だんだん成形物が硬くなると
いう欠点があった。However, these plasticizers have insufficient compatibility with the polyamide resin, and therefore have a drawback that the plasticizer leaches out and sticks to the surface of the molded product, and the plasticizer is scattered when the molded product is used at a high temperature for a long time. However, there is a drawback that the molded product becomes gradually harder.
このため、成形物にべたつきがなく、高温で長時間し
ても柔軟性を失うことのないポリアミド樹脂組成物の出
現が望まれている。For this reason, there is a demand for a polyamide resin composition which has no stickiness in a molded product and does not lose flexibility even at a high temperature for a long time.
〔課題を解決するための手段〕 本発明者らは成形物表面がべたつかず、低揮発性で柔
軟性付与効果の大きいポリアミド樹脂用可塑剤について
検討の結果、本発明を完成するに到った。[Means for Solving the Problems] The present inventors have studied the plasticizer for a polyamide resin having a low volatility and a large flexibility-imparting effect without giving a molded product a sticky surface, and have completed the present invention. .
即ち、本発明は、パラ−ヒドロキシ安息香酸またはオ
ルトーヒドロキシ安息香酸と２−オクチルオクタノー
ル、２−オクチルドデシルアルコール、２−デシルデカ
ノール、２−デシルドデシルアルコール、２−エチルデ
カノール、２−エチルドデシルアルコール及び２−オク
チル−３−オクテノールよりなる群から選ばれた分岐鎖
を有する炭素数12〜22のアルコールとのエステルをポリ
アミド樹脂100重量部当たり0.1〜30重量部配合してなる
ポリアミド樹脂組成物にかかるものである。That is, the present invention relates to para-hydroxybenzoic acid or orthohydroxybenzoic acid and 2-octyloctanol, 2-octyldodecyl alcohol, 2-decyldecanol, 2-decyldodecyl alcohol, 2-ethyldecanol, 2-ethyldecanol. Polyamide resin composition comprising an ester of an alcohol having a branched chain having 12 to 22 carbon atoms selected from the group consisting of dodecyl alcohol and 2-octyl-3-octenol, 0.1 to 30 parts by weight per 100 parts by weight of the polyamide resin It depends on the thing.
本発明において使用されるポリアミド樹脂としては （Ａ）α−ピロリドン、α−ピペリドン、ε−カプロラ
クタム、６−アミノカプロン酸、９−アミノノナン酸、
11−アミノウンデカン酸、12−アミノドデカン酸からの
重合体 （Ｂ）ヘキサメチレンジアミン，ノナメチレンジアミ
ン，ウンデカメチレンジアミン，ドデカメチレンジアミ
ン，メタキシリレンジアミン,1,4−ビス（アミノメチ
ル）シクロヘキサンなどのジアミンと アジピン酸，セバシン酸，シクロヘキサンジカルボン
酸，テレフタル酸，イソフタル酸などのジカルボン酸 とを縮重合して得られる重合体 が挙げられる。Examples of the polyamide resin used in the present invention include (A) α-pyrrolidone, α-piperidone, ε-caprolactam, 6-aminocaproic acid, 9-aminononanoic acid,
Polymers from 11-aminoundecanoic acid and 12-aminododecanoic acid (B) hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, 1,4-bis (aminomethyl) cyclohexane And a dicarboxylic acid such as adipic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid.
本発明において柔軟性付与のために配合されるパラ−
またはオルトーヒドロキシ安息香酸エステルの原料であ
るアルコールは２−オクチルオクタノール、２−オクチ
ルドデシルアルコール、２−デシルデカノール、２−デ
シルドデシルアルコール、２−エチルデカノール、２−
エチルドデシルアルコール及び２−オクチル−３−オク
テノールよりなる群から選ばれたものであり、エチル以
上の分岐鎖を有している。Para-formulated for imparting flexibility in the present invention
Alternatively, the alcohol which is the raw material of the orthohydroxybenzoate is 2-octyloctanol, 2-octyldodecyl alcohol, 2-decyldecanol, 2-decyldodecyl alcohol, 2-ethyldecanol,
It is selected from the group consisting of ethyl dodecyl alcohol and 2-octyl-3-octenol, and has a branched chain of ethyl or more.
かかるアルコールとヒドロキシ安息香酸とのエステル
は、ポリアミド樹脂との相溶性がよく、成形物表面にべ
とつきを与えることが少なく、かつ低揮発性であって、
可塑化効果も十分である。Such an ester of alcohol and hydroxybenzoic acid has good compatibility with the polyamide resin, does not give stickiness to the surface of the molded product, and has low volatility,
The plasticizing effect is also sufficient.
これに対して炭素数11以下のアルコールを原料とした
エステルは、揮発性が大きいという欠点があり、炭素数
23以上のアルコールを原料としたエステルは低揮発性で
はあるが、可塑化効果が不十分である。On the other hand, esters made from alcohols having 11 or less carbon atoms have the disadvantage that they have high volatility,
Esters made from 23 or more alcohols have low volatility, but have insufficient plasticizing effect.
また、分岐鎖を有しないアルコールを原料としたエス
テルは低揮発性と可塑化効果とを両立させることができ
ず、また成形物表面にべとつきを生ずる。更に、特開昭
48−60750号公報記載のテトラメチルノニルエステル
（メチル基を分岐鎖として含むアルコールを原料とした
エステル）でも、下記の比較例に示す如く、分岐鎖のな
いアルコールを原料とするエステルと同様の結果を示
し、不適当である。Further, an ester made of an alcohol having no branched chain cannot achieve both low volatility and a plasticizing effect, and also causes stickiness on the surface of a molded product. In addition,
In the case of the tetramethylnonyl ester (ester obtained from an alcohol containing a methyl group as a branched chain) described in JP-A-48-60750, the same results as those obtained from an ester obtained from an alcohol having no branched chain as shown in the following Comparative Examples And is inappropriate.
本発明でのヒドロキシ安息香酸エステルはパラ−また
はオルト−ヒドロキシ安息香酸と上記のアルコールと
を、無触媒あるいはSn,Ti系の触媒を使用して通常のよ
うに200〜260℃に加熱脱水して合成される。この際、酸
価が30以下になるように十分反応させることが望ましい
が、若干未反応物が残存しても差し支えない。The hydroxybenzoic acid ester in the present invention is obtained by dehydrating a para- or ortho-hydroxybenzoic acid and the above-mentioned alcohol by heating to 200 to 260 ° C. as usual using no catalyst or a Sn or Ti-based catalyst. Synthesized. At this time, it is desirable that the reaction is sufficiently performed so that the acid value becomes 30 or less, but some unreacted substances may remain.
本発明における可塑剤であるエステルはポリアミド樹
脂100重量部当たり0.1〜30重量部、好ましくは0.5〜20
重量部添加される。添加量が少ないと柔軟性が付与され
ず、添加量が多すぎると成形物の機械的強度が低下す
る。The ester as a plasticizer in the present invention is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight per 100 parts by weight of the polyamide resin.
It is added in parts by weight. If the addition amount is small, the flexibility is not imparted, and if the addition amount is too large, the mechanical strength of the molded product decreases.
本発明のポリアミド樹脂組成物は通常の押出成形、射
出成形などの方法でモノフィラメント、チューブ、ホー
スなどに成形される。The polyamide resin composition of the present invention is formed into a monofilament, a tube, a hose or the like by a usual method such as extrusion molding or injection molding.
以下に実施例により本発明を説明するが、本発明はこ
れらの実施例に限定されるものではない。Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
実施例１〜３、比較例１から７ 数平均分子量が15,000の６−ナイロン100部および本
発明の可塑剤10部をヘンシェルミキサーで混合した。こ
の混合物を押出機（220〜240℃）で溶融押出してペレッ
トとした。このペレットを射出成形機（220〜250℃）で
試験片を作成して物性測定を行った。Examples 1 to 3 and Comparative Examples 1 to 7 100 parts of 6-nylon having a number average molecular weight of 15,000 and 10 parts of the plasticizer of the present invention were mixed with a Henschel mixer. This mixture was melt-extruded with an extruder (220 to 240 ° C.) into pellets. Test pieces were prepared from the pellets using an injection molding machine (220 to 250 ° C.) and physical properties were measured.
また、可塑剤の揮発性については、直径3cm、高さ1cm
のシャーレ中に可塑剤1gを精秤して、100℃に調節した
恒温乾燥機の中に１週間保存し、重量減少を測定した。Also, regarding the volatility of the plasticizer, diameter 3 cm, height 1 cm
1 g of a plasticizer was precisely weighed in a Petri dish and stored for one week in a thermostatic dryer adjusted to 100 ° C., and the weight loss was measured.
この値の小さい方が、可塑剤の揮発性は、少ないと言
える。 It can be said that the smaller this value is, the lower the volatility of the plasticizer is.
また、成形物表面のべたつきについては、100℃に１
週間保存した試験片の表面を目視で観察する事により判
定した。In addition, the stickiness of the molded product surface was 1 degree at 100 ° C.
It was determined by visually observing the surface of the test specimen stored for a week.
成形物の引張り破断点、伸びは、ASTM D 638に従い、
成形物の曲げ強さおよび曲げ弾性率は、ASTM D 790に従
い、25℃で測定した。The tensile break point and elongation of the molded product are in accordance with ASTM D 638,
The flexural strength and flexural modulus of the molded article were measured at 25 ° C. according to ASTM D790.
これらの結果を表１に示す。 Table 1 shows the results.
表１の結果から、本発明化合物を可塑剤とした場合、
従来公知の可塑剤を使用した場合と比較して、可塑剤の
揮発性が少なく、成形品が柔軟であり、かつ成形品表面
のベタつきもないことが示された。 From the results in Table 1, when the compound of the present invention was used as a plasticizer,
As compared with the case where a conventionally known plasticizer was used, it was shown that the volatility of the plasticizer was small, the molded product was flexible, and there was no stickiness on the surface of the molded product.
Claims (1)
ヒドロキシ安息香酸と２−オクチルオクタノール、２−
オクチルドデシルアルコール、２−デシルデカノール、
２−デシルドデシルアルコール、２−エチルデカノー
ル、２−エチルドデシルアルコール及び２−オクチル−
３−オクテノールよりなる群から選ばれた分岐鎖を有す
る炭素数12〜22のアルコールとのエステルをポリアミド
樹脂100重量部当たり0.1〜30重量部配合してなるポリア
ミド樹脂組成物。(1) para-hydroxybenzoic acid or ortho-
Hydroxybenzoic acid and 2-octyloctanol, 2-
Octyldodecyl alcohol, 2-decyldecanol,
2-decyldodecyl alcohol, 2-ethyldecanol, 2-ethyldodecyl alcohol and 2-octyl-
A polyamide resin composition comprising an ester of an alcohol having 12 to 22 carbon atoms having a branched chain selected from the group consisting of 3-octenol in an amount of 0.1 to 30 parts by weight per 100 parts by weight of the polyamide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63007837A JP2582392B2 (en) | 1988-01-18 | 1988-01-18 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63007837A JP2582392B2 (en) | 1988-01-18 | 1988-01-18 | Polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01185362A JPH01185362A (en) | 1989-07-24 |
| JP2582392B2 true JP2582392B2 (en) | 1997-02-19 |
Family
ID=11676721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63007837A Expired - Fee Related JP2582392B2 (en) | 1988-01-18 | 1988-01-18 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2582392B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5789529A (en) * | 1995-06-13 | 1998-08-04 | Ube Industries, Ltd. | Polyamide resin composition and tubular molding comprising the same |
| US5783173A (en) * | 1996-11-21 | 1998-07-21 | The C. P. Hall Company | Stable sunscreen composition containing dibenzoylmethane derivative, E. G., PARSOL 1789, and C12, C16, C18, branched chain hydroxybenzoate and/or C12, C16, branched chain benzoate stabilizers/solubilizers |
| WO1998038152A1 (en) * | 1997-02-28 | 1998-09-03 | New Japan Chemical Co., Ltd. | p-HYDROXYBENZOIC ESTERS, PLASTICIZER CONTAINING THE SAME, POLYAMIDE RESIN COMPOSITION, AND MOLDED OBJECTS |
| US20030045639A1 (en) | 2001-04-18 | 2003-03-06 | Ube Industries, Ltd. | Hydraulic or pneumatic device comprising tube comprising polyamide resin |
| JP4595245B2 (en) * | 2001-05-24 | 2010-12-08 | 宇部興産株式会社 | Polyamide resin coil tube |
| JP5581694B2 (en) | 2008-01-10 | 2014-09-03 | 宇部興産株式会社 | Polyamide resin molding material and laminate using the same |
| EP3323914B1 (en) * | 2015-07-16 | 2020-01-01 | Mitsubishi Gas Chemical Company, Inc. | Polyamide resin fiber, production method for polyamide resin fiber, polyamide resin composition, woven fabric, and knitted fabric |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5415694B2 (en) * | 1971-12-03 | 1979-06-16 |
-
1988
- 1988-01-18 JP JP63007837A patent/JP2582392B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01185362A (en) | 1989-07-24 |
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