JPS6026422B2 - Thermoplastic resin composition for melt molding containing polyamide resin - Google Patents

Thermoplastic resin composition for melt molding containing polyamide resin

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Publication number
JPS6026422B2
JPS6026422B2 JP1776578A JP1776578A JPS6026422B2 JP S6026422 B2 JPS6026422 B2 JP S6026422B2 JP 1776578 A JP1776578 A JP 1776578A JP 1776578 A JP1776578 A JP 1776578A JP S6026422 B2 JPS6026422 B2 JP S6026422B2
Authority
JP
Japan
Prior art keywords
weight
resin composition
melt molding
thermoplastic resin
nitrile copolymer
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
Application number
JP1776578A
Other languages
Japanese (ja)
Other versions
JPS54110259A (en
Inventor
昌一 松村
博康 古川
雅昭 東
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.)
Kanegafuchi Chemical Industry Co Ltd
Original Assignee
Kanegafuchi Chemical Industry 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 Kanegafuchi Chemical Industry Co Ltd filed Critical Kanegafuchi Chemical Industry Co Ltd
Priority to JP1776578A priority Critical patent/JPS6026422B2/en
Publication of JPS54110259A publication Critical patent/JPS54110259A/en
Publication of JPS6026422B2 publication Critical patent/JPS6026422B2/en
Expired legal-status Critical Current

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Description

【発明の詳細な説明】 本発明は、ニトリル系共重合体とポリアミド系重合体と
から成る成形性の良好な溶融成形用熱可塑性樹脂組成物
に関する。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition for melt molding which has good moldability and is composed of a nitrile copolymer and a polyamide polymer.

従来よりゴム状重合体を含有するか、あるいは含有しな
いニトリル系共重合体が高いガスバリャー性、透明性及
び良好な機械的性質を有することが知られており、有用
な包装材などとして注目されているが、ニトリル系共重
合体の高い溶融粘度のために成形性が十分ではない。
It has been known that nitrile copolymers containing or not containing rubbery polymers have high gas barrier properties, transparency, and good mechanical properties, and have attracted attention as useful packaging materials. However, due to the high melt viscosity of nitrile copolymers, moldability is not sufficient.

これを解決せんとすれば重合の際に多量のアルキルメル
カプタン類、その他の分子量調節剤を用いたり、多量の
滑剤を配合して成形性を改良することが知られている。
しかしながら、これらの方法によると成形性の改良があ
る反面、機械的強度の低下や、ガスバリャー性の低下な
どの問題が生じると共にメルカプタン類を多量に使用す
るときにはメルカプタン類が樹脂中に残存して好ましく
ない結果をもたらす。本発明者らは、かかる欠点がない
成形性の優れたニトリル系共重合体材料を得るべく鋭意
研究した結果、ニトリル系共重合体とポリアミド系重合
体との組成物がこの目的に適することを見出し本発明に
至った。
In order to solve this problem, it is known to improve moldability by using a large amount of alkyl mercaptans or other molecular weight regulators during polymerization, or by adding a large amount of lubricant.
However, although these methods improve moldability, they also pose problems such as a decrease in mechanical strength and a decrease in gas barrier properties, and when a large amount of mercaptans is used, the mercaptans remain in the resin, making them undesirable. yields no results. As a result of intensive research to obtain a nitrile copolymer material with excellent moldability that does not have such drawbacks, the present inventors found that a composition of a nitrile copolymer and a polyamide polymer is suitable for this purpose. Heading This invention has been achieved.

本発明は、エチレン性不飽和ニトリル化合物単位を50
〜9の重量%含むニトリル系共重合体又はゴム状重合体
に上記ニトリル系共重合体をブレンドするか又はゴム状
重合体にエチレン性不飽和ニトリル化合物類をグラフト
共重合してなるニトリル系共重合体70〜9の重量%と
ポリアミド系重合体1〜3の重量%とからなる機械的性
質、ガスバリャー性、透明性のすぐれた成形性の良好な
溶融成形用熱可塑性樹脂組成物に関するものである。
The present invention has 50 ethylenically unsaturated nitrile compound units.
A nitrile copolymer obtained by blending the above nitrile copolymer with a nitrile copolymer or a rubber-like polymer containing ~9% by weight, or by graft copolymerizing an ethylenically unsaturated nitrile compound with a rubber-like polymer. The present invention relates to a thermoplastic resin composition for melt molding, which has excellent mechanical properties, gas barrier properties, transparency, and good moldability, and is composed of 70 to 9% by weight of a polymer and 1 to 3% by weight of a polyamide polymer. be.

本発明に係わるニトリル系共重合体は、一般式式中、R
は水素原子、炭素数が1〜4個のアルキル基又はハロゲ
ン原子をあらわす。
The nitrile copolymer according to the present invention has the general formula R
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.

で示されるQ,8ーオレフィン性不飽和モノニトリル単
位50〜9の重量%と、これと共重合可能な他の単量体
単位50〜1の重量%とからなる共重合体である。
It is a copolymer consisting of 50 to 9 weight % of Q,8-olefinically unsaturated mononitrile units represented by the formula and 50 to 1 weight % of other monomer units copolymerizable therewith.

エチレン性不飽和ニトリル化合物の例としては、アクリ
ロニトリル、メタクリロニトリル、エタクリロニトリル
、Q−クロルアクリルニトリル、Qーフルオロアクリロ
ニトリル、その他がある。
Examples of ethylenically unsaturated nitrile compounds include acrylonitrile, methacrylonitrile, ethacrylonitrile, Q-chloroacrylonitrile, Q-fluoroacrylonitrile, and others.

これらのうち、アクリロニトリル及びメタクリロニトリ
ルが殊に好ましい。これと共重合可能な他の単量体とし
ては、アクリル酸ェステル、メタクリル酸ェステル、ア
ルキルビニルェーテル・芳香族ビニル化合物、イソブテ
ンその他が適当であり、適当な具体例はアクリル酸メチ
ル、アクリル酸エチル、アクリル酸プチル、メタアクリ
ル酸メチル、メチルピニルエーテル、エチルビニルエー
テル、ブチルビニルエーテル、スチレン、メチルスチレ
ン、イソブテンその他である。かかるニトリル系共重合
体は、成形用熱可塑性重合体を目的として製造されたも
のであれば、いかなる方法によって製造されたものでも
よい。
Among these, acrylonitrile and methacrylonitrile are particularly preferred. Suitable other monomers that can be copolymerized with this include acrylic acid ester, methacrylic acid ester, alkyl vinyl ether/aromatic vinyl compound, isobutene, etc. Suitable specific examples include methyl acrylate, acrylic acid ester, etc. These include ethyl acid, butyl acrylate, methyl methacrylate, methyl pinyl ether, ethyl vinyl ether, butyl vinyl ether, styrene, methylstyrene, isobutene, and others. Such a nitrile copolymer may be produced by any method as long as it is produced for the purpose of being a thermoplastic polymer for molding.

上記ニトリル系共重合体は、耐衝撃性を付与するために
、ゴム状重合体を含有してもよい、ゴム状重合体を含有
させる方法は、ゴム状重合体とニトリル系共重合体とを
ブレンドする方法、ゴム状重合体の存在下でエチレン性
不飽和ニトリル化合物類をグラフト共重合する方法、前
記グラフト共重合体とニトリル系共重合体をブレンドす
る方法、その他の任意の好適な方法が採用される。ゴム
状重合体として適当なものは、ジヱン系ゴム、アクリル
酸ェステル系ゴム、オレフイン系ゴム、ウレタン系ゴム
あるいはこれらの混合物等である。これらゴム状重合体
の量は、目的に応じて任意であるが、ニトリル系共重合
体の性質を大きく損わないためには、ニトリル系共重合
体との合計に対して5の重量%以下、好ましくは2の重
量%以下がよい。本発明に使用するポリアミド系重合体
はナイロン6、ナイロン6〇 ナイロン61止 ナイロ
ン11、ナイロン12その他が挙げられる。
The above-mentioned nitrile copolymer may contain a rubbery polymer in order to impart impact resistance. A method of blending, a method of graft copolymerizing ethylenically unsaturated nitrile compounds in the presence of a rubbery polymer, a method of blending the graft copolymer and a nitrile copolymer, or any other suitable method. Adopted. Suitable rubbery polymers include diene rubber, acrylic ester rubber, olefin rubber, urethane rubber, and mixtures thereof. The amount of these rubber-like polymers is arbitrary depending on the purpose, but in order not to significantly impair the properties of the nitrile copolymer, it should not exceed 5% by weight based on the total amount with the nitrile copolymer. , preferably 2% by weight or less. Examples of the polyamide polymer used in the present invention include nylon 6, nylon 60, nylon 61, nylon 11, nylon 12, and others.

特に、ポリアミド系重合体のうち、融点が25ぴ0以下
のものが好ましく、例えばナイロン6が殊に好適である
。ポリアミド系重合体の使用量が1重量%未満であると
き成形性改良の効果に乏しく、3の重量%を超えるとき
耐衝撃性が低下することがある。それ故、ポリアミド系
重合体の使用量は、1〜3の重量%が良く、特に3〜1
5重量%が好ましい。ポリアミド系重合体は、単種で、
あるいは2種以上用いてもよく、その形状は、溶液、水
性分散液、粉夫、ベレツトなどいずれでもよい。本発明
によるニトリル系共重合体とポリアミド系重合体との混
合方法は、公3印のいかなる方法でもよく、例えば、溶
融混練、溶液ブレンド、水性分散ブレンドなどの方法が
採用される。
In particular, among polyamide polymers, those having a melting point of 25 mm or lower are preferred, and nylon 6, for example, is particularly preferred. When the amount of the polyamide polymer used is less than 1% by weight, the effect of improving moldability is poor, and when it exceeds 3% by weight, impact resistance may decrease. Therefore, the amount of polyamide polymer used is preferably 1 to 3% by weight, especially 3 to 1% by weight.
5% by weight is preferred. The polyamide polymer is a single type,
Alternatively, two or more kinds may be used, and the shape thereof may be any one such as a solution, an aqueous dispersion, a powder, and a beret. The method of mixing the nitrile copolymer and the polyamide polymer according to the present invention may be any of the commonly used methods, such as melt kneading, solution blending, aqueous dispersion blending, and the like.

射出成形、押出成形、などにより目的とする成形体とす
る場合には、加熱ロール、バンバリーミキサー、押出機
、ニーダーブレンダーその他による方法が適当である。
混合にあたっては、ニトリル系共重合体の重合反応から
、最終成形時に至るいずれの時点で実施してもよい。か
くして得た組成物は、ニトリル系共重合体の有する優れ
た性質を損うことなく、成形性が良好であり、一般の成
形機によりフィルム、シート、ボトルその他の有用な材
料を提供することが可能である。
When forming the desired molded product by injection molding, extrusion molding, etc., methods using heated rolls, Banbury mixers, extruders, kneader blenders, etc. are suitable.
The mixing may be carried out at any time from the polymerization reaction of the nitrile copolymer to the time of final molding. The composition thus obtained has good moldability without impairing the excellent properties of the nitrile copolymer, and can be produced into films, sheets, bottles, and other useful materials using general molding machines. It is possible.

以下に、実施例によって本発明を説明する。The present invention will be explained below by way of examples.

以下%とあるのはすべて重量%の意味である。実施例に
使用したニトリル系、共重合体は、スチレンープタジェ
ンの合成ゴムララツクス10%の存在下に、アクリロニ
トリル60%、スチレン20%、メチルメタアクリレー
ト10%を乳化グラフト重合し、生成した水性分散液を
常法により後処理して得たものである。実施例 1 上記のニトリル系共重合体とナイロン6(宇部興産製、
宇部ナイロン1011)とをへンシェルミキサーで混合
した後、2WCに加熱された押出機でべレツトとし、2
380で射出成形して試験片を得た。
All references to % below mean % by weight. The nitrile-based copolymer used in the examples was an aqueous dispersion produced by emulsion graft polymerization of 60% acrylonitrile, 20% styrene, and 10% methyl methacrylate in the presence of 10% styrene-butadiene synthetic rubber Larax. It was obtained by post-treating the liquid using a conventional method. Example 1 The above nitrile copolymer and nylon 6 (manufactured by Ube Industries, Ltd.)
Ube Nylon 1011) was mixed in a Henschel mixer, then made into a pellet in an extruder heated to 2WC, and
A test piece was obtained by injection molding at 380 mm.

アィゾット衝撃値は1/4インチ厚みの試験片に/ッチ
をつけ2す0で測定した。流動性は240℃で直径1側
のノズルを通過する樹脂量である。結果を第1表に示し
た。第1表 第1表に示されたように、ポリアミド(ナィロン6)の
添加により流動性は著しく改良される一方、機械的強度
、透明性は覆われない。
The Izod impact value was measured using a 1/4 inch thick test piece with a /t mark and 2s0. Fluidity is the amount of resin that passes through the nozzle on the diameter 1 side at 240°C. The results are shown in Table 1. Table 1 As shown in Table 1, the addition of polyamide (nylon 6) significantly improves flowability, but does not improve mechanical strength or transparency.

実施例 2 実施例1と同様ニトリル系共重合体とナイロン6をブレ
ンドしたが、本例ではその他にメタクリル酸メチル−プ
タジェンースチレン共重合体〔鐘淵化学工業■製、MB
S樹脂(カネェースB−松)〕を同時に加えた。
Example 2 As in Example 1, a nitrile copolymer and nylon 6 were blended, but in this example, methyl methacrylate-ptadiene-styrene copolymer [manufactured by Kanebuchi Chemical Co., Ltd., MB] was also blended.
S resin (Kanese B-Matsu)] was added at the same time.

Claims (1)

【特許請求の範囲】 1 エチレン性不飽和ニトリル化合物単位を50〜90
重量%含むニトリル系共重合体又はゴム状重合体に上記
ニトリル系共重合体をブレンドするか或いはゴム状重合
体にエチレン性不飽和ニトリル化合物類をグラフト共重
合してなるニトリル系共重合体70〜99重量%とポリ
アミド樹脂1〜30重量%とから成る溶融成形用熱可塑
性樹脂組成物。 2 エチレン性不飽和ニトリル化合物単位が一般式▲数
式、化学式、表等があります▼ (式中、Rは水素原子、炭素数が1〜4個のアルキル
基又はハロゲン原子をあらわす。 )で示されるα,β−オレフイン性不飽和モノニトリル
単位である特許請求の範囲第1項記載の溶融成形用熱可
塑性樹脂組成物。 3 ゴム状重合体の含有量が、ニトリル系共重合体との
合計に対して50重量%以下である特許請求の範囲第1
項記載の溶融成形用熱可塑性樹脂組成物。
[Claims] 1. 50 to 90 ethylenically unsaturated nitrile compound units
Nitrile copolymer 70 obtained by blending the above nitrile copolymer with a nitrile copolymer or rubber-like polymer containing % by weight, or by graft copolymerizing an ethylenically unsaturated nitrile compound with a rubber-like polymer. A thermoplastic resin composition for melt molding, comprising ~99% by weight and 1-30% by weight of a polyamide resin. 2 Ethylenically unsaturated nitrile compound units are represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom.) The thermoplastic resin composition for melt molding according to claim 1, which is an α,β-olefinically unsaturated mononitrile unit. 3. Claim 1, in which the content of the rubbery polymer is 50% by weight or less based on the total content of the nitrile copolymer.
The thermoplastic resin composition for melt molding as described in 2.
JP1776578A 1978-02-17 1978-02-17 Thermoplastic resin composition for melt molding containing polyamide resin Expired JPS6026422B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP1776578A JPS6026422B2 (en) 1978-02-17 1978-02-17 Thermoplastic resin composition for melt molding containing polyamide resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP1776578A JPS6026422B2 (en) 1978-02-17 1978-02-17 Thermoplastic resin composition for melt molding containing polyamide resin

Publications (2)

Publication Number Publication Date
JPS54110259A JPS54110259A (en) 1979-08-29
JPS6026422B2 true JPS6026422B2 (en) 1985-06-24

Family

ID=11952792

Family Applications (1)

Application Number Title Priority Date Filing Date
JP1776578A Expired JPS6026422B2 (en) 1978-02-17 1978-02-17 Thermoplastic resin composition for melt molding containing polyamide resin

Country Status (1)

Country Link
JP (1) JPS6026422B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4307207A (en) * 1980-06-26 1981-12-22 Standard Oil Company Blends of high nitrile resins and hydrophobic nylons
JPS582811U (en) * 1981-06-29 1983-01-10 日立電線株式会社 flat cable
JPH0356476U (en) * 1989-10-05 1991-05-30

Also Published As

Publication number Publication date
JPS54110259A (en) 1979-08-29

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