JPH05193060A - Plastic molded container - Google Patents
Plastic molded containerInfo
- Publication number
- JPH05193060A JPH05193060A JP755892A JP755892A JPH05193060A JP H05193060 A JPH05193060 A JP H05193060A JP 755892 A JP755892 A JP 755892A JP 755892 A JP755892 A JP 755892A JP H05193060 A JPH05193060 A JP H05193060A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- pps
- polyethylene
- gasoline
- container
- 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.)
- Withdrawn
Links
- 229920003023 plastic Polymers 0.000 title claims abstract description 11
- 239000004033 plastic Substances 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims abstract description 49
- 239000004734 Polyphenylene sulfide Substances 0.000 claims abstract description 40
- 229920000069 polyphenylene sulfide Polymers 0.000 claims abstract description 40
- -1 polyethylene Polymers 0.000 claims abstract description 26
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 21
- 239000012790 adhesive layer Substances 0.000 claims abstract description 10
- 239000003502 gasoline Substances 0.000 abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 230000004888 barrier function Effects 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000010030 laminating Methods 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 description 12
- 238000000071 blow moulding Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 125000003700 epoxy group Chemical group 0.000 description 8
- 229920000098 polyolefin Polymers 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000002828 fuel tank Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100160821 Bacillus subtilis (strain 168) yxdJ gene Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000577 Nylon 6/66 Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- TZYHIGCKINZLPD-UHFFFAOYSA-N azepan-2-one;hexane-1,6-diamine;hexanedioic acid Chemical compound NCCCCCCN.O=C1CCCCCN1.OC(=O)CCCCC(O)=O TZYHIGCKINZLPD-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は車両用燃料タンク等に用
いられるプラスチックの成形容器に関する。特にメタノ
ール混合ガソリン用タンクに適したプラスチック成形容
器に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a plastic molded container used for a vehicle fuel tank or the like. Particularly, it relates to a plastic molded container suitable for a tank for methanol-mixed gasoline.
【０００２】[0002]
【従来の技術】最近、車両用燃料タンクは、形状設計の
自由度、軽量化等の観点からポリエチレン等のプラスチ
ックを用いてブロー成形により形成することが行われて
いる。しかし、このポリエチレン製プラスチックタンク
には、ガソリン透過、すなわち、タンク内のガソリンが
外方にしみ出てくるという問題がある。2. Description of the Related Art Recently, fuel tanks for vehicles have been formed by blow molding using plastics such as polyethylene from the viewpoints of flexibility in shape design and weight reduction. However, this polyethylene plastic tank has a problem that it permeates gasoline, that is, the gasoline in the tank seeps out.
【０００３】ガソリン透過を防止する手段としては、ガ
ソリン透過の防止に効果的なポリアミド層を前述したポ
リエチレン層に積層した多層パリソンでブロー成形によ
りタンクを製造することが提案されている。すなわち、
多層パリソンをポリエチレン層、接着材層、ポリアミド
層からなる多層構造とし、これを成形型内でブロー成形
するものである。（特開昭５８−２２０７３８号公報）As a means for preventing gasoline permeation, it has been proposed to manufacture a tank by blow molding with a multilayer parison in which a polyamide layer effective for preventing gasoline permeation is laminated on the above-mentioned polyethylene layer. That is,
The multi-layer parison has a multi-layer structure including a polyethylene layer, an adhesive layer and a polyamide layer, and this is blow-molded in a molding die. (JP-A-58-220738)
【０００４】[0004]
【発明が解決しようとする課題】近年、メタノール混合
ガソリンへの世の中の要望が高まっている。メタノール
混合ガソリンに対してポリアミド層はバリヤー層として
の効果が低いために、ポリアミド層をバリヤー層とする
従来のプラスチックガソリンタンクでは不充分である。
たとえば、バリヤー層としてポリアミドを使用した容器
はガソリン１００％に対しては優れたバリヤー性能を有
するが、メタノールを１５％混合した混合ガソリンに対
してはバリヤー性能が著しく低下する。In recent years, there has been an increasing demand in the world for gasoline blended with methanol. Since the polyamide layer is less effective as a barrier layer for methanol-mixed gasoline, a conventional plastic gasoline tank having a polyamide layer as a barrier layer is insufficient.
For example, a container using polyamide as a barrier layer has an excellent barrier performance for 100% gasoline, but the barrier performance is significantly deteriorated for a mixed gasoline containing 15% methanol.
【０００５】この発明はメタノール混合ガソリンに対し
てバリヤー性能の優れたプラスチック成形容器を提供す
るものである。The present invention provides a plastic molded container having an excellent barrier performance against methanol-blended gasoline.
【０００６】[0006]
【課題を解決するための手段】この発明の特徴は、メタ
ノール混合ガソリンの透過を防止するために、バリヤー
層としてポリフェニレンスルフィド樹脂を使用する点に
ある。すなわちこの発明は、壁部が外側からポリフェニ
レンスルフィド層、接着材層、ポリエチレン層の順で相
互接着した層で構成されていることを特徴とするプラス
チック成形容器に関する。A feature of the present invention is that a polyphenylene sulfide resin is used as a barrier layer in order to prevent the permeation of methanol-blended gasoline. That is, the present invention relates to a plastic molded container characterized in that the wall portion is composed of layers in which a polyphenylene sulfide layer, an adhesive layer, and a polyethylene layer are adhered to each other in this order from the outside.
【０００７】この発明において、壁部とは容器本体を形
成する部分を意味し、底部も含まれる。この発明では、
容器の壁部が外側から上記した順に構成されていること
が重要である。ＰＰＳはポリエチレンより融点が高いの
で、ＰＰＳを最外層とするとたとえば成形時の冷却の点
において有利であり、加工しやすい。容器の内側にさら
に層を形成してもよい。In the present invention, the wall portion means a portion forming the container body, and includes the bottom portion. In this invention,
It is important that the wall of the container is constructed from the outside in the above order. Since PPS has a higher melting point than polyethylene, using PPS as the outermost layer is advantageous, for example, in terms of cooling during molding, and is easy to process. Additional layers may be formed inside the container.
【０００８】この発明の容器の壁部を構成するポリフェ
ニレンスルフィド（以下ＰＰＳと略す）とは、下記構造
式The polyphenylene sulfide (hereinafter abbreviated as PPS) constituting the wall portion of the container of the present invention has the following structural formula.
【０００９】[0009]
【化１】 [Chemical 1]
【００１０】で示される繰返し単位を７０モル％以上、
より好ましくは９０モル％以上を含む重合体である。上
記繰返し単位が７０モル％未満では耐熱性が損われるた
め好ましくない。また、ＰＰＳはその繰返し単位の３０
モル％未満を下記の構造式を有する繰返し単位などで構
成することが可能である。70 mol% or more of the repeating unit represented by
More preferably, it is a polymer containing 90 mol% or more. If the repeating unit content is less than 70 mol%, heat resistance is impaired, which is not preferable. In addition, PPS has a repeating unit of 30
Less than mol% can be composed of repeating units having the following structural formula.
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】これらのＰＰＳは、たとえば特公昭４５−
３３６８号公報や特公昭５２−１２２４０号公報に記載
された方法により得られるが、この発明では本質的に線
状で比較的高分子量のＰＰＳが好ましく用いられる。ま
た、この発明では重合後酸処理、熱水処理または有機溶
媒による洗浄により脱イオン処理を施されたＰＰＳが好
ましく用いられる。[0012] These PPS are, for example, Japanese Patent Publication No.
Although it can be obtained by the method described in Japanese Patent No. 3368 or Japanese Patent Publication No. 52-12240, essentially linear PPS having a relatively high molecular weight is preferably used in the present invention. Further, in the present invention, PPS subjected to deionization treatment by acid treatment after polymerization, hot water treatment or washing with an organic solvent is preferably used.
【００１３】ＰＰＳの他の好ましい例として、多官能性
イソシアナートで変性されたＰＰＳが挙げられる。さら
に、ＰＰＳの好ましい例として、エポキシ基含有オレフ
ィン系重合体、無水マレイン酸変性エチレン〜プロピレ
ン共重合体またはエチレン〜α，β不飽和酸アルキルエ
ステル〜無水マレイン酸共重合体を島成分とし、ＰＰＳ
を海成分とするＰＰＳ〜エラストマーアロイが挙げられ
る。Another preferred example of PPS is PPS modified with a polyfunctional isocyanate. Further, as a preferred example of PPS, an epoxy group-containing olefin polymer, a maleic anhydride-modified ethylene-propylene copolymer or an ethylene-α, β unsaturated acid alkyl ester-maleic anhydride copolymer is used as an island component, and PPS is used.
PPS-elastomer alloy having sea component as a sea component.
【００１４】この発明の容器の壁部を構成するポリエチ
レンとしては、たとえばエチレンの単独重合体、もしく
はエチレンを主体としたエチレンと他のα−オレフィ
ン、たとえばプロピレン、１−ブテン、１−ペンテン、
１−ヘキセン、４−メチル−１−ペンテン、１−オクテ
ン、１−デセン等の単独もしくは２種以上との共重合体
であって、メルトフローレート（ＪＩＳ Ｋ７２１０、
１９０℃、２１６０ｇ）が０．０１〜１ｇ／１０分、好
ましくは０．０３〜０．４ｇ／１０分、密度（ＪＩＳ
Ｋ７１１２、２３℃）が０．９１０〜０．９７０ｇ／ｃ
ｍ3 、好ましくは０．９３１〜０．９６０ｇ／ｃｍ3 の
ものが挙げられる。The polyethylene constituting the wall of the container of the present invention is, for example, a homopolymer of ethylene, or ethylene mainly composed of ethylene and other α-olefins such as propylene, 1-butene, 1-pentene,
It is a copolymer of 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or the like alone or with two or more kinds, and has a melt flow rate (JIS K7210,
190 ° C., 2160 g) is 0.01 to 1 g / 10 minutes, preferably 0.03 to 0.4 g / 10 minutes, density (JIS
K7112, 23 ° C) is 0.910 to 0.970 g / c
m 3 , preferably 0.931 to 0.960 g / cm 3 .
【００１５】この発明の容器の壁部を構成する接着材層
は、ポリエチレン層とＰＰＳ層を相互に接着させるため
のもので、用いられる接着材としては、エポキシ基含有
オレフィン系重合体、無水マレイン酸変性エチレン〜プ
ロピレン共重合体、アイオノマー、エチレン〜α，β不
飽和酸アルキルエステル〜酸無水物共重合体、カルボン
酸基含有オレフィン系重合体、無水マレイン酸変性水添
スチレン〜ブタジエンブロック共重合体および無水マレ
イン酸変性ポリエチレンなどが挙げられる。特に好まし
いのはエポキシ基含有オレフィン系重合体、エチレン〜
α，β不飽和酸アルキルエステル〜酸無水物共重合体で
ある。The adhesive layer constituting the wall of the container of the present invention is for adhering the polyethylene layer and the PPS layer to each other. The adhesive used is an epoxy group-containing olefin polymer or anhydrous maleic acid. Acid-modified ethylene-propylene copolymer, ionomer, ethylene-α, β unsaturated acid alkyl ester-acid anhydride copolymer, carboxylic acid group-containing olefin polymer, maleic anhydride-modified hydrogenated styrene-butadiene block copolymer Examples thereof include coalesce and maleic anhydride-modified polyethylene. Particularly preferred is an epoxy group-containing olefin polymer, ethylene to
It is an α, β unsaturated acid alkyl ester-acid anhydride copolymer.
【００１６】エポキシ基含有オレフィン系重合体とし
て、側鎖にグリシジルエステル、グリシジルエーテル、
グリシジルアミンなどのグリシジル基を有するオレフィ
ン系重合体や二重結合含有オレフィン系重合体の二重結
合をエポキシ酸化したものなどが挙げられる。本発明で
はこれらエポキシ基含有オレフィン系重合体のうち、α
−オレフィンとα，β−不飽和酸のグリシジルエステル
からなる共重合体が好ましく用いられる。ここでいうα
−オレフィンとしてはエチレン、プロピレンおよびブテ
ン−１などが挙げられる。また、α、β−不飽和酸のグ
リシジルエステルとは下記一般式The epoxy group-containing olefin polymer has a side chain of glycidyl ester, glycidyl ether,
Examples thereof include an olefin polymer having a glycidyl group such as glycidyl amine and a double bond-containing olefin polymer obtained by epoxy-oxidizing a double bond. In the present invention, among these epoxy group-containing olefin-based polymers, α
A copolymer composed of an olefin and a glycidyl ester of an α, β-unsaturated acid is preferably used. Α here
-Olefins include ethylene, propylene, butene-1 and the like. Further, the glycidyl ester of α, β-unsaturated acid is represented by the following general formula
【００１７】[0017]
【化３】 [Chemical 3]
【００１８】（Ｒは水素原子または低級アルキル基を示
す）で示される化合物であり、具体的にはアクリル酸グ
リシジル、メタクリル酸グリシジルおよびエタクリル酸
グリシジルなどが挙げられる。エポキシ基含有オレフィ
ン系重合体におけるエポキシ基の含有量は０．１〜３０
重量％、特に０．２〜２０重量％が好ましい。エポキシ
基含有オレフィン系重合体には、本発明の効果を損なわ
ない範囲で、他のオレフィン系モノマー、たとえばアク
リル酸メチル、メタクリル酸メチル、アクリロニトリ
ル、スチレン、酢酸ビニルおよびビニルエーテルなどを
共重合してもよい。(R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylic acid. The content of the epoxy group in the epoxy group-containing olefin polymer is 0.1 to 30.
%, Especially 0.2 to 20% by weight is preferred. The epoxy group-containing olefin-based polymer may be copolymerized with other olefin-based monomers such as methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate and vinyl ether as long as the effects of the present invention are not impaired. Good.
【００１９】エチレン〜α，β不飽和酸アルキルエステ
ル〜無水マレイン酸共重合体は、エチレンが５０〜９５
重量％、好ましくは６０〜８０重量％、α，β不飽和酸
アルキルエステルが５〜４９重量％、好ましくは７〜４
５重量％、無水マレイン酸が０．５〜１０重量％、好ま
しくは１〜８重量％からなる。α，β不飽和酸アルキル
エステルは、炭素数が３〜８個の不飽和カルボン酸、例
えば、アクリル酸、メタクリル酸等のアルキルエステル
であって、具体例としては、アクリル酸メチル、アクリ
ル酸エチル、アクリル酸ｎ−プロピル、アクリル酸イソ
プロピル、アクリル酸ｎ−ブチル、アクリル酸ｔ−ブチ
ル、アクリル酸イソブチル、メタクリル酸メチル、メタ
クリル酸エチル、メタクリル酸ｎ−プロピル、メタクリ
ル酸イソプロピル、メタクリル酸ｎ−ブチル、メタクリ
ル酸ｔ−ブチル、及びメタクリル酸イソブチル等があ
り、これらのうちでも特にアクリル酸エチル、アクリル
酸ｎ−ブチル、メタクリル酸メチルが好ましい。The ethylene-α, β unsaturated acid alkyl ester-maleic anhydride copolymer has an ethylene content of 50-95.
% By weight, preferably 60-80% by weight, α-β unsaturated acid alkyl ester 5-49% by weight, preferably 7-4
5% by weight, maleic anhydride 0.5 to 10% by weight, preferably 1 to 8% by weight. The α, β unsaturated acid alkyl ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid or methacrylic acid, and specific examples thereof include methyl acrylate and ethyl acrylate. , N-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate. , T-butyl methacrylate, isobutyl methacrylate, and the like, and among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferable.
【００２０】この発明の成形容器は、射出成形、ブロー
成形などで成形加工できるが、ブロー成形が好ましい。
以下にブロー成形による成形方法の例を図面に基づいて
説明する。図１はブロー成形の方法を示す断面図であ
る。パリソンダイ２から押出されたパリソン１は、金型
３、３′に挟まれ、その上下端部の所要部分がそれぞれ
接着されてピンチオフ部を形成し、ついでそのパリソン
内部へ空気吹込口４から空気が供給されて所定の形状に
成形される。The molded container of the present invention can be molded by injection molding, blow molding, etc., but blow molding is preferable.
An example of a molding method by blow molding will be described below with reference to the drawings. FIG. 1 is a sectional view showing a method of blow molding. The parison 1 extruded from the parison die 2 is sandwiched between the molds 3 and 3 ', and the upper and lower end portions of the parison 1 are bonded together to form a pinch-off portion. It is supplied and molded into a predetermined shape.
【００２１】図２はパリソン１の部分拡大断面図であ
る。パリソン１はその外側からＰＰＳ層１Ａ、接着材層
１Ｂ、ポリエチレン層１Ｃの順に相互に接着されてい
る。ブロー成形の場合、容器の最内層をポリエチレン層
で形成すると、ピンチオフ部がポリエチレン層の強い接
着力のもとで膨出するので、ピンチオフ部の内表面にＶ
型溝が発生することがない。FIG. 2 is a partially enlarged sectional view of the parison 1. The parison 1 is adhered to the PPS layer 1A, the adhesive layer 1B, and the polyethylene layer 1C in this order from the outside. In the case of blow molding, if the innermost layer of the container is formed of a polyethylene layer, the pinch-off portion swells due to the strong adhesive force of the polyethylene layer, so that the inner surface of the pinch-off portion is V-shaped.
No mold groove is generated.
【００２２】[0022]
【実施例】以下に実施例をあげてこの発明をさらに説明
する。The present invention will be further described with reference to the following examples.
【００２３】[0023]
【実施例１】ポリエチレンとして旭化成工業株式会社製
サンテックＢ６８０（メルトフローレート０．０５ｇ／
１０分、密度０．９５３ｇ／ｃｍ3 ）、接着材としてエ
チレン／グリシジルメタクリレート共重合体（８８／１
２重量比）、ＰＰＳとして脱イオン処理を施した直鎖状
ポリフェニレンスルフィド樹脂を用い、図１に示すブロ
ー成形方法により、容器の壁部が外面からＰＰＳ層、接
着材層、ポリエチレン層の３層からなる容器を作製し
た。[Example 1] As polyethylene, Suntech B680 (melt flow rate: 0.05 g /
10 minutes, density 0.953 g / cm 3 ), ethylene / glycidyl methacrylate copolymer (88/1) as an adhesive
2 weight ratio), using a linear polyphenylene sulfide resin that has been subjected to deionization treatment as PPS, and by the blow molding method shown in FIG. 1, the wall portion of the container has three layers of the PPS layer, the adhesive layer, and the polyethylene layer from the outer surface. A container made of was prepared.
【００２４】得られた容器に１００％ガソリン、および
メタノールを１５％含有したガソリンをそれぞれ充填
し、６０℃にて２０００時間のガソリン透過テストを行
った。重量の減少量からガソリン透過量（相対値）を求
めた結果を表１に示した。The resulting containers were filled with 100% gasoline and gasoline containing 15% of methanol, and a gasoline permeation test was carried out at 60 ° C. for 2000 hours. The results of determining the gasoline permeation amount (relative value) from the weight reduction amount are shown in Table 1.
【００２５】[0025]
【実施例２】接着材として無水マレイン酸変性ポリエチ
レを用いた以外は実施例１と同様にして３層構造の容器
を作製した。実施例１と同様にしてガソリン透過テスト
を行った結果を表１に示した。Example 2 A container having a three-layer structure was produced in the same manner as in Example 1 except that maleic anhydride-modified polyethylene was used as the adhesive. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 1.
【００２６】[0026]
【実施例３】接着材としてエチレン〜アクリル酸エステ
ル〜無水マレイン酸共重合体（住友シーディーエフ化学
社製）、ボンダインＡＸ８３９０、アクリル酸エステル
含量３２％、無水マレイン酸含量１．７５％）を使用
し、ＰＰＳとしてポリフェニレンスルフィド／ジフェニ
ルメタンジイソシアネート（１００／２）の変性ＰＰＳ
を用いた以外は、実施例１と同様にして３層構造の容器
を作製した。実施例１と同様にしてガソリン透過テスト
を行った。結果を表１に示した。Example 3 As the adhesive, ethylene-acrylic acid ester-maleic anhydride copolymer (Sumitomo CDF Chemical Co., Ltd.), Bondine AX8390, acrylic acid ester content 32%, maleic anhydride content 1.75%) are used. And modified PPS of polyphenylene sulfide / diphenylmethane diisocyanate (100/2) as PPS
A container having a three-layer structure was produced in the same manner as in Example 1 except that was used. A gasoline permeation test was conducted in the same manner as in Example 1. The results are shown in Table 1.
【００２７】[0027]
【実施例４】ＰＰＳとしてポリフェニレンスルフィド中
にエチレングリシジルメタクリレートを２０重量％島成
分として含むＰＰＳアロイを用いた以外は、実施例１と
同様にして３層構造の容器を作製した。実施例１と同様
にしてガソリン透過テストを行った結果を表１に示し
た。Example 4 A container having a three-layer structure was produced in the same manner as in Example 1 except that PPS alloy containing 20% by weight of ethyleneglycidyl methacrylate in polyphenylene sulfide as an PPS alloy was used. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 1.
【００２８】[0028]
【実施例５】ＰＰＳとして無水マレイン酸変性エチレン
〜プロピレン共重合体を２０重量％島成分として含む、
ＰＰＳアロイを用いた以外は、実施例１と同様にして３
層構造の容器を作製した。実施例１と同様にしてガソリ
ン透過テストを行った結果を表１に示した。Example 5 As a PPS, a maleic anhydride-modified ethylene-propylene copolymer is contained as an island component in an amount of 20% by weight.
3 except that the PPS alloy was used
A container having a layered structure was produced. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 1.
【００２９】[0029]
【実施例６】ＰＰＳとして、ポリフェニレンスルフィド
／ジフェニルメタンジイソシアネート（１００／２）の
変性ＰＰＳ８０重量部及びエチレン〜アクリル酸エステ
ル〜無水マレイン酸共重合体２０重量部よりなるＰＰＳ
アロイを用いた以外は、実施例３と同様にして３層構造
の容器を作製した。実施例１と同様にしてガソリン透過
テストを行った結果を表１に併せて示した。Example 6 As PPS, PPS comprising 80 parts by weight of modified PPS of polyphenylene sulfide / diphenylmethane diisocyanate (100/2) and 20 parts by weight of ethylene-acrylic ester-maleic anhydride copolymer.
A container having a three-layer structure was produced in the same manner as in Example 3 except that the alloy was used. The results of a gasoline permeation test carried out in the same manner as in Example 1 are also shown in Table 1.
【００３０】[0030]
【比較例１】ＰＰＳのかわりにナイロン６を用いた以外
は実施例１と同様の操作を行い、容器の壁部が外側から
ナイロン６層、接着材層、ポリエチレン層の３層からな
る容器を作製した。実施例１と同様にしてガソリン透過
テストを行った結果を表２に示した。[Comparative Example 1] The same operation as in Example 1 was carried out except that nylon 6 was used instead of PPS, and a container having a wall portion composed of three layers of nylon 6 layer, adhesive layer, and polyethylene layer from the outside was prepared. It was made. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 2.
【００３１】ナイロン６層をバリヤー層とした容器は、
１００％ガソリンに対しては良好なガソリン透過防止能
を有するが、メタノールを１５％混合したガソリンに対
する透過防止能はＰＰＳを使用した場合に比らべて著し
く低く、メタノール混合ガソリンに対しては適さないこ
とがわかる。A container having a nylon 6 layer as a barrier layer is
It has good gasoline permeation preventive ability against 100% gasoline, but its permeation preventive ability against gasoline containing 15% methanol is significantly lower than that using PPS, and it is suitable for methanol mixed gasoline. I know there isn't.
【００３２】[0032]
【比較例２】ＰＰＳのかわりにナイロン６６を用いた以
外は実施例２と同様の操作を行い、容器の壁部が外側か
らナイロン６６層、接着材層、ポリエチレン層の３層か
らなる容器を作製した。実施例１と同様にしてガソリン
透過テストを行った結果を表２に示した。[Comparative Example 2] The same operation as in Example 2 was carried out except that nylon 66 was used instead of PPS, and a container having a three-layered structure including a nylon 66 layer, an adhesive layer, and a polyethylene layer from the outer side was formed. It was made. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 2.
【００３３】[0033]
【比較例３】バリヤー層としてＰＰＳのかわりにナイロ
ン６／６６共重合体を用いた以外は、実施例３と同様に
して３層壁からなる容器を作製した。実施例１と同様に
してガソリン透過テストを行った結果を表２に示した。Comparative Example 3 A container having a three-layer wall was produced in the same manner as in Example 3 except that nylon 6/66 copolymer was used as the barrier layer instead of PPS. The results of a gasoline permeation test conducted in the same manner as in Example 1 are shown in Table 2.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】[0036]
【発明の効果】この発明のプラスチック成形容器は、メ
タノール混合ガソリンに対して優れたバリヤー性能を有
するので、ガソホール用タンクとして有用である。INDUSTRIAL APPLICABILITY The plastic molded container of the present invention has an excellent barrier performance against methanol-blended gasoline and is therefore useful as a tank for gasohol.
【図１】ブロー成形の方法の例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of a blow molding method.
【図２】実施例１で用いるパリソンの部分拡大断面図で
ある。FIG. 2 is a partially enlarged cross-sectional view of a parison used in Example 1.
１ パリソン ２ パリソンダイ ３ 金型 ４ 空気吹込口 1 parison 2 parison die 3 mold 4 air inlet
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｂ６５Ｄ 1/09 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location B65D 1/09
Claims (1)
ド層、接着材層、ポリエチレン層の順で相互接着した層
で構成されていることを特徴とするプラスチック成形容
器。1. A plastic molded container characterized in that the wall portion is composed of layers in which a polyphenylene sulfide layer, an adhesive layer, and a polyethylene layer are mutually adhered in this order from the outside.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP755892A JPH05193060A (en) | 1992-01-20 | 1992-01-20 | Plastic molded container |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP755892A JPH05193060A (en) | 1992-01-20 | 1992-01-20 | Plastic molded container |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05193060A true JPH05193060A (en) | 1993-08-03 |
Family
ID=11669139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP755892A Withdrawn JPH05193060A (en) | 1992-01-20 | 1992-01-20 | Plastic molded container |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05193060A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845296A3 (en) * | 2006-04-13 | 2010-01-06 | Stant Manufacturing Inc. | Multiple-layer pipe and tank for fuel |
-
1992
- 1992-01-20 JP JP755892A patent/JPH05193060A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1845296A3 (en) * | 2006-04-13 | 2010-01-06 | Stant Manufacturing Inc. | Multiple-layer pipe and tank for fuel |
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