JPS6140263B2 - - Google Patents
Info
- Publication number
- JPS6140263B2 JPS6140263B2 JP55156967A JP15696780A JPS6140263B2 JP S6140263 B2 JPS6140263 B2 JP S6140263B2 JP 55156967 A JP55156967 A JP 55156967A JP 15696780 A JP15696780 A JP 15696780A JP S6140263 B2 JPS6140263 B2 JP S6140263B2
- Authority
- JP
- Japan
- Prior art keywords
- nylon
- weight
- polyamide
- present
- parts
- 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
Links
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 20
- 229920006122 polyamide resin Polymers 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 8
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 6
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000203 mixture Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 230000006353 environmental stress Effects 0.000 description 8
- 229920000305 Nylon 6,10 Polymers 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920000572 Nylon 6/12 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 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 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- 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ポリアミド樹
脂組成物に関する。
ヘキサメチレンジアミンとアジピン酸の重縮合
反応で得られるポリキサメチレンアジパミド（以
下ナイロン66という）はその強靭性、電気特性、
耐熱性を生かして、自動車や電気製品の部品分野
に利用されているが、ナイロン66の重大な欠点の
一つに金属ハロゲン化物によつて環境応力亀裂が
生じることがあげられる。特に塩化亜鉛や塩化カ
ルシウムとの接触では、ナイロン樹脂成形品にク
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。
本発明者らは上記したナイロン66の欠点を改善
すべく鋭意検討した結果、特定の脂肪族ポリアミ
ドを特定の割合でナイロン66に配合することによ
り、金属ハロゲン化物による環境応力亀裂が著し
く改善され、しかもナイロン66が本来有する強靭
性、耐熱性等を生かした機械的性質に優れたポリ
アミド樹脂組成物が得られることを見い出し、本
発明を完成するに到つたものである。
すなわち、本発明はナイロン66 20〜80重量部
とポリマー主鎖中のメチレン基数とアミド基数の
比（ＣＨ２／ＮＨＣＯ）が６〜11である脂肪族ポリアミ
ド80
〜20重量部とを配合してな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、ナイロン66
と特定の脂肪族ポリアミドを配合した組成物であ
るが、本発明において使用するナイロン66は、そ
の結晶性を大きく損わない範囲で他のポリアミド
形成モノマーとの共重合体であつてもよい。本発
明でいう脂肪族ポリアミドとは、酸アミド結合を
有する線状合成高分子であり、主鎖中のメチレン
基数とアミド基数の比（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７、ナイロン９、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等ま
たはそれらの混合物があげられる。主鎖中のメチ
レン基数とアミド基数の比が６未満のポリアミド
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、その比が
11以上のポリアミドではナイロン66との相溶性が
損われるため、組成物の性質が損われる。
本発明のポリアミド樹脂組成物は、ナイロン66
20〜80重量部、好ましくは30〜70重量部と脂肪族
ポリアミド80〜20重量部、好ましくは70〜30重量
部からなるものである。組成物中の該脂肪族ポリ
アミドの量が20重量部より少なすぎると、金属ハ
ロゲン化物による環境応力亀裂に対する抵抗性の
改善が充分でなく、また80重量部を越えると、ナ
イロン66の有する優れた機械的性質を著しく低下
させる。
本発明の組成物は、周知の製造方法によつて製
造できるが、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於いて、こ
れら組成物にさらに他のポリアミド類や他の樹脂
ポリマー、通常の無機充填剤、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。
次に本発明を実施例により具体的に説明する。
なお実施例中の相対粘度ηｒはJIS―K6810に
基づいて硫酸溶液で測定した。
実施例 １
ペレツト状のナイロン66（相対粘度ηｒ＝
2.65）に、ペレツト状のナイロン610（相対粘度
ηｒ＝2.50）を加えて、タンブラー型混合機にて
ブレンドした後、70mmφ単軸押出機にて溶融混練
し造粒してポリアミド樹脂組成物を得た。この
際、ナイロン66に対するナイロン610の割合、す
なわちナイロン66／ナイロン610を重量比で20／
80，50／50，70／30，80／20と変化させた。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１表に示す。
比較例 １〜４
実施例１と同じナイロン66とナイロン610を用
いて、ナイロン66とナイロン610の配合割合を重
量比で100／０，90／10，10／90，０／100の割合
に混合し、実施例１と同様の方法でポリアミド組
成物を得て、耐環境応力亀裂性と引張強度を調べ
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 has few environmental stress cracks caused by metal halides and has excellent mechanical properties. Polyxamethylene adipamide (hereinafter referred to as nylon 66), which is obtained by the polycondensation reaction of hexamethylene diamine and adipic acid, has excellent toughness, electrical properties,
Due to its heat resistance, it is used in parts for automobiles and electrical products, but one of the major drawbacks of nylon 66 is that it can develop environmental stress cracks due to metal halides. In particular, contact with zinc chloride or calcium chloride is known to cause cracks in nylon resin molded products, causing deterioration of the molded products. The inventors of the present invention have made extensive studies to improve the above-mentioned drawbacks of nylon 66, and have found that by blending a specific aliphatic polyamide into nylon 66 in a specific ratio, environmental stress cracking caused by metal halides is significantly improved. Furthermore, the inventors have discovered that it is possible to obtain a polyamide resin composition with excellent mechanical properties that takes advantage of the inherent toughness and heat resistance of nylon 66, leading to the completion of the present invention. That is, the present invention blends 20 to 80 parts by weight of nylon 66 and 80 to 20 parts by weight of an aliphatic polyamide whose ratio of the number of methylene groups to the number of amide groups in the polymer main chain ( CH2 /NHCO) is 6 to 11. The present invention relates to a polyamide resin composition. The polyamide resin composition of the present invention is made of nylon 66
Nylon 66 used in the present invention may be a copolymer with other polyamide-forming monomers as long as its crystallinity is not significantly impaired. The aliphatic polyamide used in the present invention is a linear synthetic polymer having an acid amide bond, and is a polyamide in which the ratio of the number of methylene groups to the number of amide groups in the main chain (CH 2 /NHCO is 6 to 11). Polyamides include nylon 7, nylon 9, nylon 11, and nylon.
12, nylon 69, nylon 610, nylon 612, etc., or mixtures thereof. In polyamides in which the ratio of the number of methylene groups to the number of amide groups in the main chain is less than 6, the contribution of metal halides to improving resistance to environmental stress cracking is insufficient;
Polyamides with a molecular weight of 11 or more impair compatibility with nylon 66, thereby impairing the properties of the composition. The polyamide resin composition of the present invention is made of nylon 66
It consists of 20 to 80 parts by weight, preferably 30 to 70 parts by weight, and 80 to 20 parts by weight, preferably 70 to 30 parts by weight of the aliphatic polyamide. If the amount of the aliphatic polyamide in the composition is less than 20 parts by weight, the resistance to environmental stress cracking caused by metal halides will not be improved sufficiently, and if it exceeds 80 parts by weight, the excellent properties of nylon 66 will not be improved. Significantly reduces mechanical properties. The composition of the present invention can be manufactured by well-known manufacturing methods, such as melt blending in an extruder such as a conventional single-screw or twin-screw extruder, blending by injection molding, etc. It will be done. In addition, to the extent that the purpose of the present invention is not impaired, these compositions may further contain other polyamides, other resin polymers, ordinary inorganic fillers, colorants, oxidative deterioration inhibitors, heat stabilizers, and ultraviolet absorbers. , antistatic agent,
A lubricant, plasticizer, flame retardant, etc. can be added depending on the purpose. Next, the present invention will be specifically explained using examples. Note that the relative viscosity ηr in the examples was measured using a sulfuric acid solution based on JIS-K6810. Example 1 Pellet-like nylon 66 (relative viscosity ηr=
2.65), pellet-shaped nylon 610 (relative viscosity ηr = 2.50) was added and blended in a tumbler type mixer, then melt-kneaded and granulated in a 70 mmφ single screw extruder to obtain a polyamide resin composition. Ta. At this time, the ratio of nylon 610 to nylon 66, that is, the weight ratio of nylon 66/nylon 610 is 20/
It was changed to 80, 50/50, 70/30, and 80/20. 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 1. Comparative Examples 1 to 4 Using the same nylon 66 and nylon 610 as in Example 1, the weight ratio of nylon 66 and nylon 610 was 100/0, 90/10, 10/90, 0/100. A polyamide composition was obtained in the same manner as in Example 1, and its environmental stress cracking resistance and tensile strength were examined. The results are shown in Table 1.
【表】
実施例 ２〜４
実施例１で用いたナイロン66に、ナイロン11
（相対粘度ηｒ＝2.45）、ナイロン12（相対粘度η
ｒ＝2.34）及びナイロン612（相対粘度ηｒ＝
2.68）を重量比で50対50の割合で配合し、実施例
１と同様の方法でポリアミド組成物を得て諸物性
を調べた。その結果を第２表に示す。
比較例 ５〜７
実施例１で用いたナイロン66にナイロン６（相
対粘度ηｒ＝2.37）を重量比でナイロン６／ナイ
ロン66＝75／25，50／50，25／75と変えて配合
し、実施例１と同様の方法でポリアミド組成物を
得た。その結果を第２表に示す。[Table] Examples 2 to 4 Nylon 11 was added to the nylon 66 used in Example 1.
(relative viscosity ηr=2.45), nylon 12 (relative viscosity η
r=2.34) and nylon 612 (relative viscosity ηr=
2.68) in a weight ratio of 50:50, a polyamide composition was obtained in the same manner as in Example 1, and various physical properties were investigated. The results are shown in Table 2. Comparative Examples 5 to 7 Nylon 6 (relative viscosity ηr = 2.37) was blended with the nylon 66 used in Example 1 with the weight ratio changed to nylon 6/nylon 66 = 75/25, 50/50, 25/75, A polyamide composition was obtained in the same manner as in Example 1. The results are shown in Table 2.
【表】
第１表、第２表より明らかなように、本発明の
組成物は金属ハロゲン化物による環境応力亀裂が
非常に少なく、かつ機械的性質が優れていること
を示している。[Table] As is clear from Tables 1 and 2, the composition of the present invention shows very little environmental stress cracking due to metal halides and excellent mechanical properties.
Claims (1)
とポリマー主鎖中のメチレン基数とアミド基数の
比（ＣＨ２／ＮＨＣＯ）が６〜11である脂肪族ポリアミ
ド80 〜20重量部とを配合してなるポリアミド樹脂組成
物。[Claims] 1. 20 to 80 parts by weight of polyhexamethylene adipamide and 80 to 20 parts by weight of an aliphatic polyamide in which the ratio of the number of methylene groups to the number of amide groups in the polymer main chain (CH 2 /NHCO) is 6 to 11. A polyamide resin composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55156967A JPS5780449A (en) | 1980-11-10 | 1980-11-10 | Polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55156967A JPS5780449A (en) | 1980-11-10 | 1980-11-10 | Polyamide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5780449A JPS5780449A (en) | 1982-05-20 |
| JPS6140263B2 true JPS6140263B2 (en) | 1986-09-08 |
Family
ID=15639229
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55156967A Granted JPS5780449A (en) | 1980-11-10 | 1980-11-10 | Polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5780449A (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 (13)
| 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 |
| JPS58168654A (en) * | 1982-03-30 | 1983-10-05 | Nippon Denso Co Ltd | Plastic molding for automobile |
| JPS60248775A (en) * | 1984-05-24 | 1985-12-09 | Teijin Ltd | Resin composition |
| JPS63308064A (en) * | 1988-04-13 | 1988-12-15 | Toray Ind Inc | Top and base of automotive radiator |
| JPS63295664A (en) * | 1988-04-13 | 1988-12-02 | Toray Ind Inc | Tube for automobile pipe |
| JPS63304053A (en) * | 1988-04-13 | 1988-12-12 | Toray Ind Inc | Part for exhaust gas system for automobile |
| JPS63289063A (en) * | 1988-04-13 | 1988-11-25 | Toray Ind Inc | Automobile cylinder head cover |
| JPS63289064A (en) * | 1988-04-13 | 1988-11-25 | Toray Ind Inc | Automobile oil pan |
| JPS63304052A (en) * | 1988-04-13 | 1988-12-12 | Toray Ind Inc | Cooling fan for automobile |
| JP4779416B2 (en) * | 2004-04-20 | 2011-09-28 | 宇部興産株式会社 | Polyamide resin composition |
| JP4444723B2 (en) * | 2004-04-20 | 2010-03-31 | 豊田合成株式会社 | Plastic molded product |
| BR112012024187B1 (en) | 2010-03-30 | 2019-12-31 | Basf Se | use of thermoplastic molding materials, and, molding |
| JP7092026B2 (en) * | 2016-12-01 | 2022-06-28 | 東洋紡株式会社 | Polyamide resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50158647A (en) * | 1974-06-14 | 1975-12-22 | ||
| JPS5318667A (en) * | 1976-08-04 | 1978-02-21 | Toyo Boseki | Stretching polyamid film |
| JPS551299A (en) * | 1979-06-04 | 1980-01-08 | Mitsubishi Heavy Ind Ltd | Life raft pouring device of ship |
-
1980
- 1980-11-10 JP JP55156967A patent/JPS5780449A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50158647A (en) * | 1974-06-14 | 1975-12-22 | ||
| JPS5318667A (en) * | 1976-08-04 | 1978-02-21 | Toyo Boseki | Stretching polyamid film |
| JPS551299A (en) * | 1979-06-04 | 1980-01-08 | Mitsubishi Heavy Ind Ltd | Life raft pouring device of ship |
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 |
|---|---|
| JPS5780449A (en) | 1982-05-20 |
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