JPH051304B2 - - Google Patents
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- Publication number
- JPH051304B2 JPH051304B2 JP58196110A JP19611083A JPH051304B2 JP H051304 B2 JPH051304 B2 JP H051304B2 JP 58196110 A JP58196110 A JP 58196110A JP 19611083 A JP19611083 A JP 19611083A JP H051304 B2 JPH051304 B2 JP H051304B2
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- relative viscosity
- polyamide
- weight
- 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.)
- Expired - Lifetime
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はポリアミド樹脂組成物に関する。さら
に詳しくは金属ハロゲン化物による環境応力亀裂
が少なく、かつ機械的性質に優れた、層状体成形
品を提供するポリアミド樹脂組成物に関する。
ポリアミドはその強靱性、電気特性、耐熱性を
生かして、自動車や電気製品の部品として巾広く
利用されている。しかし、汎用的に用いられてい
るポリアミド、例えばε−カプロラクタムの開環
重合で得られるナイロン６やヘキサメチレンジア
ミンとアジピン酸の重縮合反応で得られるナイロ
ン66など、では金属ハロゲン化物によつて環境応
力亀裂が生じるという重大な欠点がある。特に塩
化亜鉛や塩化カルシウムとの接触では、ポリアミ
ド樹脂成形品にクラツクを生じ成形品の劣化を引
き起こすことが知られている。
この環境応力亀裂を改善するため、研究がなさ
れており、ナイロン66に高級脂肪酸ポリアミドを
配合することが効果的であることが知られてい
る。（特開昭57−80449、特開昭57−212252）。
本発明者らは、更にこの問題を改善すべく鋭意
検討した結果、ナイロン66〔Ａ〕に、高級脂肪族
ポリアミド〔Ｂ〕を配合するに際し〔Ａ〕と
〔Ｂ〕の分子量（相対溶液粘度）を特定すること
が、驚くべきことに、この改善に大きな効果を発
揮することを見出した。
又、当該組成物は層状体を為していることが、
倍率14倍の顕微鏡写真で確認されており、本発明
はこの層状体を、当該環境応力亀裂改善に効果あ
らしめるものにしたものである。
すなわち、本発明は、ナイロン66〔Ａ〕30〜60
重量部と（CH2／NHCO）が６〜11の高級脂肪
族ポリアミド〔Ｂ〕70〜40重量部とからなり、か
つ〔Ａ〕の相対粘度が4.0〜5.0であり、〔Ａ〕と
〔Ｂ〕の相対粘度比（〔Ａ〕の相対粘度／〔Ｂ〕の
相対粘度）が1.50〜2.50であるポリアミド樹脂組
成物に関するものである。
本発明のポリアミド樹脂組成物は、２種の脂肪
族ポリアミドからなる組成物であるが、この種別
は、ポリマー主鎖中のメチレン基数とアミド基数
の比（CH2／NHCO）で行うことができる。ナ
イロン66〔Ａ〕は、（CH2／NHCO）が５である
ポリアミドである。
高級脂肪族ポリアミド〔Ｂ〕は、（CH2／
NHCO）が、６〜11であるポリアミドであり、
かかるポリアミドとしては、ナイロン11、ナイロ
ン12、ナイロン69、ナイロン610、ナイロン612、
ナイロン613等またはそれらの混合物、共重合体
があげられる。
〔Ｂ〕においてその比が12以上の場合は、〔Ａ〕
と〔Ｂ〕との相溶性が損われ、組成物の性質が損
われる。
本発明において使用するナイロン66〔Ａ〕と高
級脂肪族ポリアミド〔Ｂ〕の相対粘度比は1.50〜
2.50である。1.50未満では、金属ハロゲン化物に
よる環境応力亀裂に対する抵抗性改善への寄与が
不充分であり、2.50を越えると押出し、成形加工
性が悪く実用的でない。又、ナイロン66〔Ａ〕の
相対粘度は4.0〜5.0のものである。
ここでいう相対粘度とは、JIS Ｋ−6810に基づ
いて測定した相対粘度をいう。
本発明のポリアミド樹脂組成物は、ナイロン66
〔Ａ〕と高級脂肪族ポリアミド〔Ｂ〕の粘度比が
1.50〜2.50となるよう選ばれ、ナイロン66〔Ａ〕
30〜60重量部とポリアミド〔Ｂ〕70〜40重量部か
らなるものである。
組成物中の脂肪族ポリアミド〔Ｂ〕の量が40重
量部より少ないと、金属ハロゲン化物による環境
応力亀裂に対しての改善が充分でなく、又70重量
部を越えると、ナイロン66〔Ａ〕の有する機械的
性質を低下させる。
本発明の組成物は、周知の製造方法によつて製
造できる。例えば常用の単軸または二軸押出機の
ような、押出機中で溶融ブレンドする方法、射出
成形でブレンドする方法等が挙げられる。
また本発明の目的を損わない範囲において、こ
れら組成物にさらに他の樹脂ポリマー、着色剤、
酸化劣化防止剤、熱安定剤、紫外線吸収剤、帯電
防止剤、滑剤、可塑剤、難燃剤などを目的に応じ
て添加することができる。
このように本発明は極めて特徴的である。即
ち、先に公開された文献（特開昭57−80449、特
開昭57−212252）には、ナイロン66〔Ａ〕に高級
脂肪族ポリアミド〔Ｂ〕を配合することが示され
ているが、〔Ａ〕，〔Ｂ〕の相対粘度比に言及され
ていない。
これに対して、本発明は、〔Ａ〕30〜60重量部
と〔Ｂ〕70〜40重量部からなる配合組成におい
て、〔Ａ〕の相対粘度を4.0〜5.0として、且つ
〔Ａ〕と〔Ｂ〕の相対粘度比を1.50〜2.50にする
ことが、環境応力亀裂に効果大なることを見いだ
したものであり、全く新規な発明である。
次に本発明を実施例により具体的に説明する。
実施例１、比較例１
相対粘度ηrが2.58，3.80，4.01，4.78のナイロ
ン66と相対粘度ηrが2.18，2.76のナイロン610を
第１表に示す組み合わせにて、ナイロン66にナイ
ロン610を重量比で60対40の割合で加え、タンブ
ラー型混合機にてブレンドした。当混合物を
70mnφ単軸押出機にて溶融混練しポリアミド樹
脂組成物を得た。得られたポリアミド組成物を射
出成形機を用いて物性測定用試験片に成形し、耐
環境応力亀裂性を調べた。その結果を第１表に示
す。
比較例 ２
相対粘度ηrが2.58，4.78，6.00のナイロン66と
相対粘度ηrが1.70，2.26，2.76のナイロン610を第
１表に示す組み合わせにして、ナイロン66にナイ
ロン610を重量比で60対40の割合で加え、実施例
１と同様の方法でポリアミド組成物を得て、耐環
境応力亀裂性を調べた。その結果を第１表に示
す。
The present invention relates to polyamide resin compositions. More specifically, the present invention relates to a polyamide resin composition that provides a layered molded product that has few environmental stress cracks caused by metal halides and has excellent mechanical properties. Polyamide is widely used as parts of automobiles and electrical products due to its toughness, electrical properties, and heat resistance. However, commonly used polyamides, such as nylon 6 obtained by ring-opening polymerization of ε-caprolactam and nylon 66 obtained from the polycondensation reaction of hexamethylene diamine and adipic acid, are environmentally friendly due to metal halides. A significant drawback is the formation of stress cracks. In particular, contact with zinc chloride or calcium chloride is known to cause cracks in polyamide resin molded products and cause deterioration of the molded products. Research has been conducted to improve this environmental stress cracking, and it is known that blending higher fatty acid polyamide with nylon 66 is effective. (Japanese Patent Publication No. 57-80449, Japanese Patent Application Publication No. 57-212252). As a result of intensive studies to further improve this problem, the present inventors found that when blending higher aliphatic polyamide [B] with nylon 66 [A], the molecular weights (relative solution viscosity) of [A] and [B] Surprisingly, we have found that identifying this has a great effect on this improvement. Further, the composition has a layered structure,
This was confirmed in a micrograph at a magnification of 14 times, and the present invention makes this layered material effective in improving the environmental stress cracking. That is, the present invention uses nylon 66 [A] 30-60
parts by weight and 70 to 40 parts by weight of higher aliphatic polyamide [B] having (CH 2 /NHCO) of 6 to 11, and [A] has a relative viscosity of 4.0 to 5.0, and [A] and [B] The present invention relates to a polyamide resin composition having a relative viscosity ratio (relative viscosity of [A]/relative viscosity of [B]) of 1.50 to 2.50. The polyamide resin composition of the present invention is a composition consisting of two types of aliphatic polyamides, and this type can be determined by the ratio of the number of methylene groups to the number of amide groups (CH 2 /NHCO) in the polymer main chain. . Nylon 66 [A] is a polyamide in which (CH 2 /NHCO) is 5. Higher aliphatic polyamide [B] is (CH 2 /
NHCO) is 6 to 11,
Such polyamides include nylon 11, nylon 12, nylon 69, nylon 610, nylon 612,
Examples include nylon 613, mixtures and copolymers thereof. If the ratio in [B] is 12 or more, [A]
The compatibility between and [B] is impaired, and the properties of the composition are impaired. The relative viscosity ratio of nylon 66 [A] and higher aliphatic polyamide [B] used in the present invention is 1.50 to
It is 2.50. If it is less than 1.50, the contribution of the metal halide to improving resistance to environmental stress cracking is insufficient, and if it exceeds 2.50, extrusion and moldability are poor and it is not practical. Further, the relative viscosity of nylon 66 [A] is 4.0 to 5.0. The relative viscosity here refers to the relative viscosity measured based on JIS K-6810. The polyamide resin composition of the present invention is made of nylon 66
The viscosity ratio of [A] and higher aliphatic polyamide [B] is
Selected to be 1.50 to 2.50, nylon 66 [A]
It consists of 30 to 60 parts by weight and 70 to 40 parts by weight of polyamide [B]. If the amount of aliphatic polyamide [B] in the composition is less than 40 parts by weight, the improvement against environmental stress cracking caused by metal halides will not be sufficient, and if it exceeds 70 parts by weight, nylon 66 [A] Decreases the mechanical properties of The composition of the present invention can be manufactured by a well-known manufacturing method. Examples include a method of melt blending in an extruder such as a conventional single-screw or twin-screw extruder, a method of blending by injection molding, and the like. In addition, other resin polymers, colorants,
Oxidative deterioration inhibitors, heat stabilizers, ultraviolet absorbers, antistatic agents, lubricants, plasticizers, flame retardants, etc. can be added depending on the purpose. In this way, the present invention is extremely distinctive. That is, previously published documents (JP-A-57-80449, JP-A-57-212252) indicate that higher aliphatic polyamide [B] is blended with nylon 66 [A]; There is no mention of the relative viscosity ratio of [A] and [B]. On the other hand, in the present invention, in a compounding composition consisting of 30 to 60 parts by weight of [A] and 70 to 40 parts by weight of [B], the relative viscosity of [A] is set to 4.0 to 5.0, and [A] and [ It has been found that setting the relative viscosity ratio of B] to 1.50 to 2.50 is highly effective against environmental stress cracking, and this is a completely new invention. Next, the present invention will be specifically explained using examples. Example 1, Comparative Example 1 Nylon 66 with a relative viscosity ηr of 2.58, 3.80, 4.01, 4.78 and nylon 610 with a relative viscosity ηr of 2.18, 2.76 are combined as shown in Table 1, and the weight ratio of nylon 610 to nylon 66 is They were added at a ratio of 60:40 and blended using a tumbler type mixer. This mixture
A polyamide resin composition was obtained by melt-kneading using a 70 mnφ single-screw extruder. The obtained polyamide composition was molded into a test piece for measuring physical properties using an injection molding machine, and its resistance to environmental stress cracking was examined. The results are shown in Table 1. Comparative Example 2 Nylon 66 with a relative viscosity ηr of 2.58, 4.78, 6.00 and nylon 610 with a relative viscosity ηr of 1.70, 2.26, 2.76 were combined as shown in Table 1, and the weight ratio of nylon 66 to nylon 610 was 60:40. A polyamide composition was obtained in the same manner as in Example 1, and its environmental stress cracking resistance was examined. The results are shown in Table 1.
【表】【table】
【表】
実施例 ２
ペレツト状のナイロン66（相対粘度ηr＝4.01）
にペレツト状のナイロン612（相対粘度ηr＝2.22）
を加えて、実施例−１と同様の方法でポリアミド
樹脂組成物を得た。この際、ナイロン66／ナイロ
ン612を重量比で35／65，50／50の組成物を作成
した。得られたポリアミド組成物を射出成形機を
用いて物性測定用試験片に成形し、耐環境応力亀
裂性と引張強度を調べた。その結果を第２表に示
す。
比較例 ３
実施例−２と同じナイロン66とナイロン612を
用いて、ナイロン66とナイロン612の配合割合を
重量比で重量比で100／０，95／５，85／15，
70／30，25／75，15／85，５／95，０／100の割
に混合し、実施例−２と同様の方法でポリアミド
組成物を得て、実施例−２と同様に評価した。そ
の結果を第２表に示す。[Table] Example 2 Nylon 66 in pellet form (relative viscosity ηr=4.01)
Nylon 612 in pellet form (relative viscosity ηr=2.22)
was added to obtain a polyamide resin composition in the same manner as in Example-1. At this time, compositions with a weight ratio of nylon 66/nylon 612 of 35/65 and 50/50 were prepared. The obtained polyamide composition was molded into a test piece for measuring physical properties using an injection molding machine, and its environmental stress cracking resistance and tensile strength were examined. The results are shown in Table 2. Comparative Example 3 Using the same nylon 66 and nylon 612 as in Example-2, the weight ratio of nylon 66 and nylon 612 was 100/0, 95/5, 85/15,
A polyamide composition was obtained by mixing in proportions of 70/30, 25/75, 15/85, 5/95, and 0/100 in the same manner as in Example-2, and evaluated in the same manner as in Example-2. . The results are shown in Table 2.
Claims (1)
NHCO）が６〜11の高級脂肪族ポリアミド〔Ｂ〕
70〜40重量部とからなり、かつ〔Ａ〕の相対粘度
が4.0〜5.0であり、〔Ａ〕と〔Ｂ〕の相対粘度比
（〔Ａ〕の相対粘度／〔Ｂ〕の相対粘度）が1.50〜
2.50であることを特徴とするポリアミド樹脂組成
物。[Claims] 1. 30 to 60 parts by weight of nylon 66 [A], and (CH 2 /
Higher aliphatic polyamide with NHCO) of 6 to 11 [B]
70 to 40 parts by weight, and the relative viscosity of [A] is 4.0 to 5.0, and the relative viscosity ratio of [A] and [B] (relative viscosity of [A] / relative viscosity of [B]) is 1.50〜
2.50. A polyamide resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19611083A JPS6088066A (en) | 1983-10-21 | 1983-10-21 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19611083A JPS6088066A (en) | 1983-10-21 | 1983-10-21 | Polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6088066A JPS6088066A (en) | 1985-05-17 |
| JPH051304B2 true JPH051304B2 (en) | 1993-01-07 |
Family
ID=16352401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19611083A Granted JPS6088066A (en) | 1983-10-21 | 1983-10-21 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6088066A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013101891A1 (en) | 2011-12-30 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Polyamide composition containing ionomer |
| US8906479B2 (en) | 2011-12-30 | 2014-12-09 | E I Du Pont De Nemours And Company | Compositions of polyamide and ionomer |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19634399A1 (en) * | 1996-08-26 | 1998-03-05 | Basf Ag | Cosmetic with polymer-bound benzophenone chromophores |
| DE19634401A1 (en) * | 1996-08-26 | 1998-03-05 | Basf Ag | Cosmetic with polymer-bound benzophenone chromophores |
| WO2011120949A1 (en) | 2010-03-30 | 2011-10-06 | Basf Se | Use of polyamides that are resistant to corrosion and stress cracking |
| JP2017203151A (en) * | 2016-05-06 | 2017-11-16 | 旭化成株式会社 | Polyamide resin composition and method for improving chemical resistance |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57212252A (en) * | 1981-06-25 | 1982-12-27 | Ube Ind Ltd | Polyamide composition resistant to calcium chloride |
-
1983
- 1983-10-21 JP JP19611083A patent/JPS6088066A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013101891A1 (en) | 2011-12-30 | 2013-07-04 | E. I. Du Pont De Nemours And Company | Polyamide composition containing ionomer |
| US8906479B2 (en) | 2011-12-30 | 2014-12-09 | E I Du Pont De Nemours And Company | Compositions of polyamide and ionomer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6088066A (en) | 1985-05-17 |
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