JPH01272436A - Hollow blow container made of polyamide resin - Google Patents
Hollow blow container made of polyamide resinInfo
- Publication number
- JPH01272436A JPH01272436A JP63102974A JP10297488A JPH01272436A JP H01272436 A JPH01272436 A JP H01272436A JP 63102974 A JP63102974 A JP 63102974A JP 10297488 A JP10297488 A JP 10297488A JP H01272436 A JPH01272436 A JP H01272436A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- ethylene
- ester copolymer
- acid
- 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.)
- Pending
Links
- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 25
- 229920001577 copolymer Polymers 0.000 claims abstract description 18
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000011342 resin composition Substances 0.000 claims abstract 3
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000005977 Ethylene Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 230000004888 barrier function Effects 0.000 abstract description 6
- -1 cyclic lactam Chemical class 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004677 Nylon Substances 0.000 abstract description 3
- 229920002292 Nylon 6 Polymers 0.000 abstract description 3
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 239000000155 melt Substances 0.000 abstract description 3
- 229920001778 nylon Polymers 0.000 abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 238000000071 blow moulding Methods 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229920000554 ionomer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 241001147388 Uncia Species 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical group CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 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
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IVNAZOGVWDHYGU-UHFFFAOYSA-L C(CCCCCCCCC(=O)[O-])(=O)[O-].[Ag+2] Chemical compound C(CCCCCCCCC(=O)[O-])(=O)[O-].[Ag+2] IVNAZOGVWDHYGU-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920009181 Novamid® 1030 Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- MRDFUOGXMCUGJP-UHFFFAOYSA-N [Ag+3].P([O-])([O-])[O-] Chemical compound [Ag+3].P([O-])([O-])[O-] MRDFUOGXMCUGJP-UHFFFAOYSA-N 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポリアミド樹脂本来の優れた耐薬品性に加え
て、ガスバリア性が高く衝撃特性も良好なポリアミド樹
脂製中空ブロー容器を提供するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a hollow blow container made of polyamide resin that has high gas barrier properties and good impact properties in addition to the excellent chemical resistance inherent to polyamide resin. It is.
ポリアミド樹脂製ブロー容器は、耐薬品性と機械的特性
に優れており、種々の薬品、オイル、溶剤等を保存する
容器として広く使用されている０
しかしながら、ポリアミド樹脂はプロー成形性に劣り、
また容器としての耐衝撃性に劣るため、例えばアイオノ
マー樹脂やニトリルゴム（時開ｒ３−ｉｏｔｏ弘ｒ）を
配合することが試みられている。Blow containers made of polyamide resin have excellent chemical resistance and mechanical properties, and are widely used as containers for storing various chemicals, oils, solvents, etc.0 However, polyamide resin has poor blow moldability,
In addition, since the impact resistance as a container is poor, attempts have been made to blend, for example, ionomer resin or nitrile rubber (Jikikai R3-IOTO Hiroshi).
ところが、ニトリルゴムを配合するとプロー成形時の熱
劣化が著しくなり、アイオノマー樹脂等のオレフィン系
共重合体を配合す□ると、ガス透過性が著しく低下する
、という欠点があった０
従って、ガスバリア性が高く、衝撃特性に優実状であっ
た。However, when nitrile rubber is blended, thermal deterioration during blow molding becomes significant, and when olefin copolymers such as ionomer resins are blended, gas permeability is significantly reduced. It had high strength and excellent impact properties.
本発明者らは、上記問題を解決すべく鋭意研究を重ねた
結果、エチレン・アクリル酸エステル共重合体を配合し
たポリアミド樹脂を使用することによって、プロー成形
性が著しく向上し、ガスバリヤ性も維持出来ることを見
出した。また、エチレンとアクリル酸エステルとの共重
合体をポリアミドに配合しても、通常の射出成形品にお
いては耐衝撃性は改良されないが（特公昭≠ｒ−／ ７
＆ ｉ！： ！ ；比較例−ｊなど）、ブロー成形品例
おいては、驚くべきことに顕著な衝撃性改良効果がある
ことを見出し、本発明に到達したものである。As a result of intensive research aimed at solving the above problems, the present inventors found that by using a polyamide resin blended with an ethylene/acrylic acid ester copolymer, blow moldability was significantly improved and gas barrier properties were also maintained. I found out what I can do. Furthermore, even if a copolymer of ethylene and acrylic ester is blended with polyamide, the impact resistance of ordinary injection molded products will not be improved (Tokukosho≠r-/7
&i! : ! ; Comparative Example-j, etc.) and blow-molded product examples, it was surprisingly found that there was a remarkable effect of improving impact properties, and the present invention was achieved based on this finding.
すなわち本発明は、ブロー成形性に優れ、耐衝撃性とガ
スバリア性の良好なポリアミド樹脂製中空ブロー容器を
提供することを目的としたものであり、その要旨は、
ポリアミド樹脂； 乙Ｏ〜９０重量％、エチレン・アク
リル酸
エステル共重合体；
４Ｌｏ−２重量％、
からなるポリアミド樹脂組成物を成形してなる、ポリア
ミド樹脂製中空ブロー容器に存する。That is, the present invention aims to provide a hollow blow container made of polyamide resin with excellent blow moldability and good impact resistance and gas barrier properties, and the gist thereof is as follows: Polyamide resin; %, ethylene/acrylic acid ester copolymer; 4Lo-2% by weight.
本発明において使用されるポリアミドとじては、３員環
以上のラクタム、重合可能なω−アミノ酸、二塩基酸と
ジアミンなどの重縮合によって得られるポリアミドを用
いることができる。As the polyamide used in the present invention, polyamides obtained by polycondensation of lactams having three or more membered rings, polymerizable ω-amino acids, dibasic acids, diamines, etc. can be used.
具体的には、ε−カプロラクタム、アミノカプロン酸、
エナントラクタム、７−アミノへブタン酸、／／−アミ
ノウンデカン酸、ターアミノノナン酸、α−ピロリドン
、α−ピペリドンなどの重合体、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な
どのジアミンと、テレフタル酸、イン７タル酸、アジピ
ン酸、セパチン酸、ドデカンニ塩基酸、ゲルタール酸な
どのジカルボン酸と重縮合せしめて得られる重合体また
はこれらの共重合体、例えば、ナイロン≠、’％ ７
１ ｇ、／Ｉ、 ／２、６．乙、 ６．り、 乙、／
０． ４．／ ／。Specifically, ε-caprolactam, aminocaproic acid,
Polymers such as enantholactam, 7-aminohbutanoic acid, //-aminoundecanoic acid, teraminononanoic acid, α-pyrrolidone, α-piperidone, hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine , a polymer obtained by polycondensing a diamine such as metaxylylene diamine with a dicarboxylic acid such as terephthalic acid, in7thalic acid, adipic acid, cepatic acid, dodecane dibasic acid, geltal acid, or a copolymer thereof; For example, nylon≠, '%7
1 g, /I, /2,6. B, 6. ri, otsu, /
0. 4. / /.
７、／ ｊ、Ｊ ’ｌ”、 ｔ／ｌ、ｔ、６／／２、
ｔ／１ｒｆｘどがあげられる。7, / j, J 'l'', t/l, t, 6//2,
Examples include t/1rfx.
こうしたポリアミド樹脂の中でも、ナイロン６、ナイロ
ン６．６またはこれらの共重合体を使用した場合に好ま
しい結果が得られる。Among these polyamide resins, preferable results are obtained when nylon 6, nylon 6.6, or copolymers thereof are used.
本発明に適用するポリアミド樹脂としては、相対粘度（
ＪＩＳ Ｋ−ｔｒｔｏに基き、９０係硫酸中で測定した
値）が２．！〜６．！とぐにａ、Ｏ〜６．０のものが好
ましい。上記範囲よりも相対粘度（以下ηｒｅｌ と
略称する）が小さいポリアミド樹脂を使用すると、ブロ
ー成形性が阻害され、また上記範囲よりもηｒｅｌの大
きなポリアミド樹脂を使用すると、ブロー容器の肉厚が
不均一になり、更にはゲル状の異物が発生することもあ
る。The polyamide resin applied to the present invention has a relative viscosity (
Based on JIS K-trto, the value measured in 90% sulfuric acid) is 2. ! ~6. ! It is preferable to have a value of a of 0 to 6.0. If a polyamide resin with a relative viscosity (hereinafter abbreviated as ηrel) smaller than the above range is used, blow moldability will be inhibited, and if a polyamide resin with a larger ηrel than the above range is used, the wall thickness of the blow container will be uneven. In addition, gel-like foreign matter may occur.
本発明で用いられるエチレン・アクリル酸エステル系共
重合体は、エチレン単位が？０〜６０重量係、重量しく
は♂！〜ｊｊ重量係で重量、アクリル酸エステル（メタ
クリル酸エステルを含む。）単位としては、１ｏ−ｓｏ
重重量、好ましくは／ｊ−≠ｊ重重量％ある。エチレン
拳アクリル酸エステル系共重合体のメルトインデックス
（ＡＳＴＭ ＤＩ−２３ｒ に準拠して測定）は１〜１
００９７１０分、好ましくはｔ 〜ｊ。The ethylene/acrylic acid ester copolymer used in the present invention has ethylene units? 0-60 weight section, weight is ♂! ~jj Weight, acrylic ester (including methacrylic ester) unit: 1o-so
by weight, preferably /j-≠j% by weight. The melt index of the ethylene fist acrylic ester copolymer (measured according to ASTM DI-23r) is 1 to 1.
009710 minutes, preferably t~j.
２／／０分である。遊離のアクリル酸が存在すると、ポ
リアミド樹脂と反応してゲルが生じるため、遊離のアク
リル酸は１％以下、好ましくはＯｊ％とする必要がある
。2//0 minutes. If free acrylic acid is present, it will react with the polyamide resin to form a gel, so the content of free acrylic acid must be 1% or less, preferably Oj%.
本発明において好適に用いられる市販品としては、日本
ユニカ■製、ＢＲＴ−≠９０（商標）が挙げられる。As a commercially available product suitably used in the present invention, BRT-≠90 (trademark) manufactured by Nippon Unica ■ may be mentioned.
ポリアミド樹脂とエチレン晦アクリル酸エステル系共重
合体との配合は当該業者に周知の方法で行なわれ、具体
的には、押出機、ルーダ−、バンバリーミキサ−等が使
用される。また、均一混合したペレットをあらかじめ混
練することなく、ブロー成形の際に直接成形機内で混練
し、次いで成形する方法も採ることが出来る。The blending of the polyamide resin and the ethylene acrylate copolymer is carried out by a method well known to those skilled in the art, and specifically, an extruder, Ruder, Banbury mixer, etc. are used. Alternatively, it is also possible to knead the homogeneously mixed pellets directly in a molding machine during blow molding, without kneading them in advance, and then mold the pellets.
本発明における組成物には、更に周知の種々の添加剤、
例えばガラス繊維、炭素繊維、金属ウィスカーのような
補強剤、シリカ、アルミナ、シリカ−アルミナ系粘土鉱
物、シリカ−マグネシウム系粘土鉱物、ケイ酸カルシウ
ム、炭酸カルシウム、アスベスト、カーボンブラックの
ような充填剤、その他滑剤、核剤、酸化防止剤、難燃剤
、帯電防止剤、耐候付与剤等を含有してもよい。The composition of the present invention further includes various well-known additives,
For example, reinforcing agents such as glass fibers, carbon fibers, metal whiskers, fillers such as silica, alumina, silica-alumina clay minerals, silica-magnesium clay minerals, calcium silicate, calcium carbonate, asbestos, carbon black, In addition, it may contain a lubricant, a nucleating agent, an antioxidant, a flame retardant, an antistatic agent, a weathering agent, etc.
また、ブロー成形品のピンチオフ強度を高めるために、
周知の酸化防止剤を配合することが更に好ましい。なか
でも銅化合物をポリアミド樹脂とエチレン・アクリル酸
エステル共重合体との組成物７００重量部に対し、０．
００１〜／、０重量部配合することが有効である。In addition, to increase the pinch-off strength of blow molded products,
It is further preferable to incorporate a well-known antioxidant. Among them, 0.00 parts by weight of the copper compound is added to 700 parts by weight of the composition of polyamide resin and ethylene/acrylic acid ester copolymer.
It is effective to blend 001 to 0 parts by weight.
銅化合物としては、ポリアミド樹脂に均一配合可能なも
のであれば特に制限はなく、ヨウ化銅、塩化第一銅、塩
化第二銅、臭化第一銅、臭化第二銅のようなハロゲン化
銅、ギ酸銅、酢酸鋼、プロピオン酸銅、ステアリン酸銅
、シュウ酸銅、セバシン酸銀、乳酸銀、安息香酸銅、サ
リチル酸銅のような有機酸銅、硫酸銅、硝酸銅、燐酸銅
、亜燐酸銀のような無機酸銅、あるいは銅キレート化合
物などがあげられるが、ヨウ化銅、塩化第一銅などが好
適である。There are no particular restrictions on the copper compound as long as it can be uniformly blended into the polyamide resin, and halogens such as copper iodide, cuprous chloride, cupric chloride, cuprous bromide, and cupric bromide may be used. Organic acids such as copper chloride, copper formate, steel acetate, copper propionate, copper stearate, copper oxalate, silver sebacate, silver lactate, copper benzoate, copper salicylate, copper sulfate, copper nitrate, copper phosphate, Examples include inorganic copper acids such as silver phosphite, copper chelate compounds, and copper iodide, cuprous chloride, and the like are preferred.
本発明のプロー成形は、当該業者に周知の方法によって
行なわれ、ブロー成形機の能力や成形品の形状等に特に
制約は無く、従来から既知の方法を利用することができ
る。The blow molding of the present invention is carried out by a method well known to those skilled in the art, and there are no particular restrictions on the capacity of the blow molding machine, the shape of the molded product, etc., and conventionally known methods can be used.
すなわち、−船釣には通常のプロー成形機を用いてパリ
ソンを形成後、適当な温度でプロー成形を行なえばよい
。That is, - For boat fishing, a parison may be formed using a normal blow molding machine, and then blow molding may be performed at an appropriate temperature.
以下、実施例によって本発明を具体的に説明するが、本
発明はその要旨を逸脱しない限りこれに限定されるもの
ではない。なお、評価法は次の通りである。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto unless it departs from the gist thereof. The evaluation method is as follows.
（１） 肉厚の均一性
シリンダー径≠０ｒｔａφの押出ブロー成形機にて直径
３０瓢φのダイスを用い、長さ３００朋直径♂Ｏｍφの
容器をプロー成形し、側面において上端から２０ｒｔｍ
、下端から２０鱈の部位の肉厚を測定した。(1) Uniformity of wall thickness A container with a length of 300mm and a diameter of ♂Omφ is blow-molded using an extrusion blow molding machine with a cylinder diameter≠0rtaφ using a die with a diameter of 30mmφ.
The wall thickness of 20 parts of the cod from the bottom was measured.
（２）落下試験
上述のブロー成形品に３００ ｃｃの水を入れ、成形品
と同一材料にて射出成形したキャップにより密封し、コ
ンクリート床上に／ｍの高さからくり返し落下させ、成
形品が破損するまでの回数を測定した。(2) Drop test The above blow molded product was filled with 300 cc of water, sealed with an injection molded cap made of the same material as the molded product, and repeatedly dropped onto a concrete floor from a height of /m, causing damage to the molded product. The number of times it took to do so was measured.
（３） 薬品透過性
上述のブロー容器に３００２のメチルシクロヘキサンを
入れ、成形品と同一材料を用いて射出成形したキャップ
の内側にエポキシ樹脂接着剤を塗布後、キャップをしめ
て密封し、５０℃恒温槽内にｌＱ日間放置して、重量減
少を測定した。(3) Chemical permeability Place 3002 methylcyclohexane in the above-mentioned blow container, apply epoxy resin adhesive to the inside of the cap injection-molded using the same material as the molded product, close the cap, seal it, and keep it at a constant temperature of 50℃. It was left in the tank for 1Q days and the weight loss was measured.
（４） ガス透過性
押出機径弘０ｒｒａφのＴダイ製膜機を用い、０．７醪
厚のシートを製膜し、１０ＯＸ１００間の大きさにカッ
トして、炭酸ガス透過率測定装置（ＰＥＲＭＡＴＲＡＮ
Ｃ−■； ＭｏｄｅｒｎＣｏｎｔｒｏｌｓ Ｉｎｃ
、製）にて２３℃における炭酸ガスの透過率を測定した
。(4) Using a T-die film forming machine with a gas permeability extruder diameter of 0rraφ, a sheet with a thickness of 0.7 is formed, cut into a size between 10OX100, and a carbon dioxide gas permeability measuring device (PERMATRAN).
C-■; Modern Controls Inc.
The permeability of carbon dioxide gas at 23° C. was measured at 23°C.
（５） Ｉｚｏｄ衝撃値
１７２インチ厚みの試験片を用い、ＡＳＴＭ［）−２ｊ
Ｊに準じて行った。(5) Izod impact value using a 172 inch thick test piece, ASTM [)-2j
I followed J.
実施例／〜３
オストワルド粘度計による相対粘度弘、５の市販ナイロ
ン６樹脂（三菱化成■製； Ｎｏｖａｍｉｄ１０３０）
及び、エチレン単位が７！係、アクリル酸エチルが２ｊ
（１）メルトインデックスが２０ ？／／ ０分の市販
のエチレン・アクリル酸エステル共重合体（日本ユニカ
■製； ＢＲＴ−弘りＯ）を、表−７の配合比になるよ
うに混合し、樹脂温度コ２Ｏ−２ｔＯ℃にて、１０１φ
押出機で溶融混練し、得られたベレットを１２０℃にて
２弘時間真空乾燥後、プロー成形を行って、肉厚の均一
性、落下試験、薬品透過性を測定した。Example/~3 Relative viscosity measured by Ostwald viscometer, 5 commercially available nylon 6 resin (manufactured by Mitsubishi Kasei; Novamid 1030)
And 7 ethylene units! In charge, ethyl acrylate is 2j
(1) Is the melt index 20? // 0 minute commercially available ethylene/acrylic acid ester copolymer (manufactured by Nippon Unica ■; BRT-Hiroshi O) was mixed at the blending ratio shown in Table 7, and the resin temperature was raised to 2O-2tO℃. So, 101φ
The pellets obtained by melt-kneading in an extruder were vacuum-dried at 120° C. for 2 hours, followed by blow molding, and the uniformity of wall thickness, drop test, and chemical permeability were measured.
また、上記樹脂混合物について射出成形品における効果
を見るため、型締カフ ｊ ｔｏｎの射出成形機を用い
、射出成形して、得られた試験片について、Ｉｚｏｄ衝
撃値を測定した。Further, in order to examine the effect of the above resin mixture on injection molded products, injection molding was performed using a mold-clamping injection molding machine, and the Izod impact value was measured for the obtained test pieces.
更に、Ｔダイ製膜機でフィルムを作成し、炭酸ガス透過
性を測定した。Furthermore, a film was created using a T-die film forming machine, and its carbon dioxide permeability was measured.
これらの測定結果は表−２に示した。These measurement results are shown in Table-2.
比較例１
エチレン・アクリル酸エステル共重合体を除いたほかは
、実施例１〜３と同様に行った。各種物性の測定結果を
表−２に示した。Comparative Example 1 The same procedure as Examples 1 to 3 was carried out except that the ethylene/acrylic acid ester copolymer was removed. The measurement results of various physical properties are shown in Table 2.
比較例２〜３
エチレン・アクリル酸エステル共重合体の代わりに、エ
チレン系共重合体としてアイオノマー樹脂（デュポン社
製：サーリン／７０４）、若しくはエチレン・グリシジ
ルメタクリレート共重合体（住友化学製； Ｂｏｎｄ
Ｆａｓｔ ２Ｂ）を使用した他は、実施例／〜３と同様
に行った。配合比は表−／に示した通りである。Comparative Examples 2 to 3 Instead of the ethylene/acrylic ester copolymer, an ionomer resin (manufactured by DuPont: Surlyn/704) or an ethylene/glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical; Bond) was used as an ethylene copolymer.
Fast 2B) was used in the same manner as in Examples/~3. The blending ratio is as shown in Table 1.
実施例／〜３と同様にして行なった各種物性の測定結果
は、表−２に示した。The results of measurements of various physical properties conducted in the same manner as in Examples/--3 are shown in Table 2.
実施例から明らかなように、ポリアミド樹脂とエチレン
・アクリル酸エステル共重合体からなる中空ブロー容器
は、均一な肉厚が得られ、耐衝撃性に優れ、しかもガス
バリヤ性が良好である。As is clear from the examples, the hollow blow container made of polyamide resin and ethylene/acrylic acid ester copolymer has a uniform wall thickness, excellent impact resistance, and good gas barrier properties.
Claims (1)
ミド樹脂製中空ブロー容器。(1) A polyamide resin hollow blow container formed by molding a polyamide resin composition consisting of a polyamide resin; 60 to 90% by weight and an ethylene/acrylic acid ester copolymer; 40 to 2% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63102974A JPH01272436A (en) | 1988-04-26 | 1988-04-26 | Hollow blow container made of polyamide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63102974A JPH01272436A (en) | 1988-04-26 | 1988-04-26 | Hollow blow container made of polyamide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01272436A true JPH01272436A (en) | 1989-10-31 |
Family
ID=14341719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63102974A Pending JPH01272436A (en) | 1988-04-26 | 1988-04-26 | Hollow blow container made of polyamide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01272436A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308454A (en) * | 1988-06-06 | 1989-12-13 | Tokai Rubber Ind Ltd | Gas-impermeable resin composition |
| WO2015165361A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Nylon powder composition for 3d printing, and preparation method and use thereof |
-
1988
- 1988-04-26 JP JP63102974A patent/JPH01272436A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01308454A (en) * | 1988-06-06 | 1989-12-13 | Tokai Rubber Ind Ltd | Gas-impermeable resin composition |
| WO2015165361A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Nylon powder composition for 3d printing, and preparation method and use thereof |
| US11472929B2 (en) | 2014-04-30 | 2022-10-18 | Institute Of Chemistry, Chinese Academy Of Sciences | Nylon powder composition for 3D printing, and preparation method and application thereof |
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