JPH10202804A - Laminated body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body with excellent adhesive strength of an adhesive layer and which can be used for a fuel conveyance, pipe for gasoline, etc., by forming the adhesive layer which is placed between both resin layers and bonds integrally them together with a mixed compsn. contg. polymethyl methacrylate-grafted polyethylene and polymethyl methacrylate. SOLUTION: A cylindrical inner layer 2 is formed of a polyvinylidene fluoride resin and an outer layer 3 is formed of a polyethylene resin and these are integrally bonded together with an adhesive layer 4 placed between the inner layer 2 and the outer layer 3 to form a cylindrical laminated material 1. Here, the adhesive layer 4 is formed with a mixed compsn. wherein a polymethyl methacrylate-grafted polyethylene and a polymethyl methacrylate are mixed in such a way that wt. ratio of the sum of polyethylene and polymethyl methacrylate in the polymethyl methacrylate-grafted polyethylene and polyethylene in the polymethyl methacrylate-grafted polyethylene is a specified value.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、ガソリン等の燃料
輸送管や貯蔵タンクとして使用される積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate used as a fuel transport pipe or storage tank for gasoline or the like.

【０００２】[0002]

【従来の技術】安価であるが、ガソリン等の油分や農薬
などの耐薬品性の点で問題があるポリエチレンやポリプ
ロピレン等のポリオレフィン樹脂と、耐薬品性等には優
れるが比較的高価であるフッ素樹脂との互いの欠点を補
うべく、接液される内面側にフッ素樹脂層を有し、外面
にこのフッ素樹脂層の保護および補強のためにポリオレ
フィン樹脂層を設けた積層体が特公昭６０−４３３０７
号公報や特公昭６４−１２２２９号公報等において提案
されている。2. Description of the Related Art Polyolefin resins, such as polyethylene and polypropylene, which are inexpensive but have a problem in terms of resistance to oils such as gasoline and agricultural chemicals, and fluorine, which is excellent in chemical resistance but relatively expensive. In order to compensate for each other's drawbacks with the resin, a laminate having a fluororesin layer on the inner surface to be in contact with the liquid and a polyolefin resin layer on the outer surface for protection and reinforcement of the fluororesin layer is disclosed in 43307
And Japanese Patent Publication No. 64-12229.

【０００３】また、これらの積層体は、ポリオレフィン
樹脂とフッ素樹脂との間に接着性がないため、ポリオレ
フィン樹脂層とフッ素樹脂層との間に、ポリオレフィン
樹脂およびフッ素樹脂のいずれにも接着性を有する接着
層を設け、両樹脂層を積層一体化するようにしている。
しかし、これら従来の積層体の場合、液の膨張や液量の
変化などにより内層側から受ける圧力変化が大きいガソ
リン等の燃料輸送管に用いると、接着層の接着力が十分
と言えず、層間剥離を起こして管閉塞を招く恐れがあ
る。[0003] Further, since these laminates have no adhesiveness between the polyolefin resin and the fluororesin, the adhesiveness between the polyolefin resin layer and the fluororesin layer is given to both the polyolefin resin and the fluororesin. Is provided so that both resin layers are laminated and integrated.
However, in the case of these conventional laminates, when used for a fuel transport pipe of gasoline or the like, which undergoes a large pressure change from the inner layer due to expansion of the liquid or a change in the amount of the liquid, the adhesive strength of the adhesive layer cannot be said to be sufficient. Peeling may occur and blockage of the pipe may be caused.

【０００４】[0004]

【発明が解決しようとする課題】本発明は、このような
事情に鑑みて、接着層の接着強度に優れ、ガソリン等の
燃料輸送管としても十分な使用に耐える積層体を提供す
ることを目的としている。SUMMARY OF THE INVENTION In view of the foregoing, an object of the present invention is to provide a laminate which has an excellent adhesive strength of an adhesive layer and which can be sufficiently used as a fuel transport pipe for gasoline or the like. And

【０００５】[0005]

【課題を解決するための手段】本発明にかかる積層体
は、このような目的を達成するために、ポリエチレン系
樹脂層と、ポリフッ化ビニリデン系樹脂層と、この両樹
脂層の間に介在し、両樹脂層を接着一体化する接着層と
を備える積層体において、前記接着層が、ポリメタクリ
ル酸メチルをグラフト化したポリエチレンとポリメタク
リル酸メチルとを含む混合組成物で形成されている構成
とした。In order to achieve such an object, a laminate according to the present invention comprises a polyethylene resin layer, a polyvinylidene fluoride resin layer, and a resin layer interposed between the two resin layers. A laminate comprising an adhesive layer for bonding and integrating both resin layers, wherein the adhesive layer is formed of a mixed composition containing polyethylene and polymethyl methacrylate grafted with polymethyl methacrylate. did.

【０００６】上記構成において、ポリエチレン（以下、
「ＰＥ」と記す）系樹脂としては、低密度、直鎖状低密
度、中密度、高密度等のＰＥ等の一般のＰＥおよびこれ
らのＰＥにＰＥ自体の物性を損なわない程度で他の成分
が共重合或いはグラフト重合しているものが挙げられ
る。ポリフッ化ビニリデン（以下、「ＰＶＤＦ」と記
す）系樹脂としては、ジフルオロエチレンモノマーから
重合されるポリマーであれば特に制限はなく、このポリ
マーにポリマーの物性を損なわない範囲で他の成分が含
まれていても構わない。In the above structure, polyethylene (hereinafter, referred to as polyethylene)
As the “PE” -based resin, general-purpose PEs such as low-density, linear low-density, medium-density, and high-density PEs and other components to such an extent that the physical properties of the PEs themselves are not impaired. Are copolymerized or graft-polymerized. The polyvinylidene fluoride (hereinafter, referred to as “PVDF”) resin is not particularly limited as long as it is a polymer polymerized from a difluoroethylene monomer, and other components are included in this polymer as long as the physical properties of the polymer are not impaired. It does not matter.

【０００７】ポリメタクリル酸メチルをグラフト化した
ポリエチレン（以下、「ＰＥ−ｇＰＭＭＡ」と記す）と
は、ＰＥを主鎖としてポリメタクリル酸メチル（以下、
「ＰＭＭＡ」と記す）がグラフトしているものである。
また、各層には、必要に応じて物性を損なわない範囲で
滑剤、導電剤、紫外線吸収剤等の添加剤を添加してもよ
い。Polyethylene grafted with polymethyl methacrylate (hereinafter referred to as “PE-gPMMA”) is a polymethyl methacrylate (hereinafter, referred to as “PE-gPMMA”) having PE as a main chain.
"PMMA").
Further, additives such as a lubricant, a conductive agent, and an ultraviolet absorber may be added to each layer as needed as long as the physical properties are not impaired.

【０００８】さらに、接着層を形成する混合組成物中、
ＰＥ−ｇＰＭＭＡとＰＭＭＡとを、ＰＥ−ｇＰＭＭＡ中
のＰＭＭＡを含むＰＭＭＡの総和と、ＰＥ−ｇＰＭＭＡ
中のＰＥとの重量比で、ＰＭＭＡの総和／ＰＥ＝３５／
６５〜９０／１０（より好ましくは４５／５５〜８０／
２０）の割合で混合しておくことが好ましい。すなわ
ち、ＰＭＭＡの総和／ＰＥが３５／６５より小さいと、
ＰＶＤＦ系樹脂層と接着層との界面で剥離する恐れがあ
り、ＰＭＭＡの総和／ＰＥが９０／１０より大きいと、
ＰＥ系樹脂層と接着層との界面で剥離する恐れがある。Further, in the mixed composition for forming the adhesive layer,
PE-gPMMA and PMMA, the sum of PMMA including PMMA in PE-gPMMA, PE-gPMMA
The total weight of PMMA / PE = 35 /
65-90 / 10 (more preferably 45 / 55-80 /
It is preferable to mix at a ratio of 20). That is, when the sum of PMMA / PE is smaller than 35/65,
If there is a risk of peeling at the interface between the PVDF-based resin layer and the adhesive layer, and if the total PMMA / PE is larger than 90/10,
There is a risk of peeling at the interface between the PE-based resin layer and the adhesive layer.

【０００９】ＰＥ−ｇＰＭＭＡのグラフト率は、１０〜
２３０％程度が好ましい。また、平均分子量は１０００
〜５０００００程度が好ましい。The graft ratio of PE-gPMMA is 10
About 230% is preferable. The average molecular weight is 1000
About 500,000 is preferable.

【００１０】なお、本発明の積層体は、ＰＥ系樹脂層が
外層となり、ＰＶＤＦ系樹脂層が内層となる管状に成形
することが好ましい。積層体の製造方法としては、従来
の公知の方法が使用され、たとえば、３台の押出機より
１台の金型に各層を構成する樹脂を押し出し、金型内で
各層を合流させ３層状で金型より吐出させる共押出の方
法等が挙げられる。It is preferable that the laminate of the present invention is formed into a tubular shape in which the PE-based resin layer becomes the outer layer and the PVDF-based resin layer becomes the inner layer. As a manufacturing method of the laminate, a conventionally known method is used. For example, a resin constituting each layer is extruded into one mold from three extruders, and the respective layers are merged in the mold to form a three-layer form. A co-extrusion method of discharging from a mold and the like can be mentioned.

【００１１】[0011]

【発明の実施の形態】以下に、本発明の実施の形態を、
図面を参照しつつ詳しく説明する。図１は本発明にかか
る積層体の実施の形態をあらわしている。DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be described below.
This will be described in detail with reference to the drawings. FIG. 1 shows an embodiment of a laminate according to the present invention.

【００１２】図１に示すように、この積層体１は、管状
になっていて、内層２がＰＶＤＦ系樹脂で形成され、外
層３がＰＥ系樹脂で形成され、内層２と外層３とが、両
層２，３の間に介在する接着層４を介して接着一体化さ
れている。また、接着層４がＰＥ−ｇＰＭＭＡとＰＭＭ
Ａとを、ＰＥ−ｇＰＭＭＡ中のＰＭＭＡを含むＰＭＭＡ
の総和と、ＰＥ−ｇＰＭＭＡ中のＰＥとの重量比で、Ｐ
ＭＭＡの総和／ＰＥ＝３５／６５〜９０／１０となるよ
うに混合した混合組成物で形成されている。As shown in FIG. 1, the laminate 1 is tubular, the inner layer 2 is formed of a PVDF resin, the outer layer 3 is formed of a PE resin, and the inner layer 2 and the outer layer 3 are The two layers 2 and 3 are bonded and integrated via an adhesive layer 4 interposed therebetween. The adhesive layer 4 is made of PE-gPMMA and PMM.
A and PMMA containing PMMA in PE-gPMMA
And the weight ratio of PE to PE in PE-gPMMA, P
It is formed of a mixed composition mixed such that the sum of MMA / PE = 35/65 to 90/10.

【００１３】この積層体１は、以上のように、接着層４
として上記の混合組成物を用いたため、内層２および外
層３が接着層４を介してしっかりと接着一体化され、ガ
ソリン等の燃料配管として用いても、内部流体の圧力変
化などにより層間剥離を起こしたりすることがない。し
たがって、管閉塞などの事故を確実に防止することがで
きる。As described above, the laminated body 1 has the adhesive layer 4
Since the above-mentioned mixed composition is used, the inner layer 2 and the outer layer 3 are firmly adhered and integrated through the adhesive layer 4, and even when used as a fuel pipe such as gasoline, delamination occurs due to a change in pressure of the internal fluid. Or not. Therefore, accidents such as pipe blockage can be reliably prevented.

【００１４】[0014]

【実施例】以下に、本発明の実施例をより詳しく説明す
る。Embodiments of the present invention will be described below in more detail.

【００１５】（実施例１）ＰＥ（住友化学工業社製、ス
ミカセンＦ１０１−１）、ＰＥ−ｇＰＭＭＡ（日本油脂
社製、モディパーＡ１２００、ＰＥ／ＰＭＭＡ＝７０／
３０）７０重量部とＰＭＭＡ（住友化学工業社製、スミ
ペックス−Ｂ ＭＨＯ）３０重量部とからなる混合組成
物、および、ＰＶＤＦ（三菱化学社製、カイナー７３
０）の各原料を、３台のシングル押出機にそれぞれ供給
し、３台の押出機の先を連結するように配置された金型
に外側からＰＥ、混合組成物、ＰＶＤＦの順の層構成と
なるように各原料を押出機から押し出したのち、金型口
金から吐出した管状体をフォーミング管および冷却槽に
通し冷却賦形したのち、引取機で引取り、内径５０mm、
外径５８mm、ＰＥ層厚み３．４mm、ＰＶＤＦ層厚み０．
３mm、および、接着層としての混合組成物層厚み０．３
mmの管を得た。Example 1 PE (Sumitomo Chemical Co., Ltd., Sumikasen F101-1), PE-gPMMA (Nippon Yushi Co., Ltd., Modiper A1200, PE / PMMA = 70 /
30) A mixed composition comprising 70 parts by weight and 30 parts by weight of PMMA (Sumipex-B MHO manufactured by Sumitomo Chemical Co., Ltd.), and PVDF (Kyner 73 manufactured by Mitsubishi Chemical Corporation)
0) Each raw material is supplied to three single extruders, respectively, and a layered structure of PE, mixed composition, and PVDF is applied from the outside to a die arranged so as to connect the tips of the three extruders. After extruding each raw material from the extruder so as to form, the tubular body discharged from the mold die is passed through a forming tube and a cooling bath, cooled and shaped, and then taken up by a take-off machine, and the inner diameter is 50 mm.
Outer diameter 58mm, PE layer thickness 3.4mm, PVDF layer thickness 0.
3 mm, and a thickness of the mixed composition layer as an adhesive layer of 0.3
mm tubes were obtained.

【００１６】（実施例２）混合組成物のＰＥ−ｇＰＭＭ
ＡとＰＥとの混合割合をＰＥ−ｇＰＭＭＡ３０重量部、
ＰＥ７０重量部とした以外は、実施例１と同様にして管
を得た。（実施例３）混合組成物のＰＥ−ｇＰＭＭＡと
ＰＥとの混合割合をＰＥ−ｇＰＭＭＡ８０重量部、ＰＥ
２０重量部とした以外は、実施例１と同様にして管を得
た。Example 2 PE-gPMM of mixed composition
The mixing ratio of A and PE is 30 parts by weight of PE-gPMMA,
A tube was obtained in the same manner as in Example 1 except that the amount of PE was changed to 70 parts by weight. (Example 3) The mixing ratio of PE-gPMMA and PE in the mixed composition was 80 parts by weight of PE-gPMMA, PE
A tube was obtained in the same manner as in Example 1 except that the amount was 20 parts by weight.

【００１７】（比較例１）混合組成物に代えて、ＰＥ−
ｇＰＭＭＡのみを接着層として用いた以外は、実施例１
と同様にして管を得た。Comparative Example 1 Instead of the mixed composition, PE-
Example 1 except that only gPMMA was used as the adhesive layer.
A tube was obtained in the same manner as described above.

【００１８】上記実施例１〜３および比較例１で得た各
管の一端を密閉状態にし、他端から真空ポンプで内部の
空気を吸引し管内を−７６０mmHgまで減圧し、それぞれ
減圧状態を保ちながら１０日間保持し、その後管内を常
圧に戻して層間の剥離状況を調べ、その結果を表１にＰ
Ｅ−ｇＰＭＭＡとＰＥとの混合割合および混合組成物中
のＰＭＭＡの総和とＰＥとの重量比を合わせて示した。
なお、表１中、接着性は、層間剥離なしを○、層間剥離
ありを×であらわした。One end of each of the tubes obtained in Examples 1 to 3 and Comparative Example 1 was sealed, and the inside air was sucked from the other end by a vacuum pump to reduce the pressure in the tubes to -760 mmHg. While maintaining the pressure in the tube to normal pressure and examining the state of delamination between layers. The results are shown in Table 1.
The mixing ratio of E-gPMMA and PE and the total weight of PMMA in the mixed composition and the weight ratio of PE are shown together.
In Table 1, the adhesiveness was represented by を for no delamination, and × for delamination.

【００１９】[0019]

【表１】 [Table 1]

【００２０】表１から本発明の積層体によれば、接着層
の接着性が優れ層間剥離の問題もなく、ガソリン等の輸
送配管として優れた性能を示すことがよく分かる。な
お、本発明にかかる積層体は、上記の実施例に限定され
ない。たとえば、上記の実施例では、積層体が管に成形
されていたが、容器状に成形されても構わない。Table 1 clearly shows that the laminate of the present invention has excellent adhesiveness of the adhesive layer, has no problem of delamination, and exhibits excellent performance as a transportation pipe for gasoline and the like. Note that the laminate according to the present invention is not limited to the above embodiments. For example, in the above embodiment, the laminate is formed into a tube, but may be formed into a container.

【００２１】[0021]

【発明の効果】本発明にかかる積層体は、以上のように
構成されているので、ＰＥ系樹脂層とＰＶＤＦ系樹脂層
とが接着層を介して接着性よく接合一体化されたものと
なる。また、接着層の混合組成物を請求項２のような混
合割合にすると、より接着層の接着性が安定し、安全性
等が高くなる。The laminate according to the present invention is constructed as described above, so that the PE-based resin layer and the PVDF-based resin layer are bonded and integrated with good adhesiveness via an adhesive layer. . Further, when the mixed composition of the adhesive layer is set to the mixing ratio as in claim 2, the adhesiveness of the adhesive layer is more stabilized, and the safety and the like are improved.

【００２２】さらに，積層体を請求項３のような管状に
すれば、ガソリン等の燃料輸送管としても有効に利用す
ることができる。Further, if the laminate is formed in a tubular shape as described in claim 3, it can be effectively used as a fuel transport pipe for gasoline and the like.

【図面の簡単な説明】[Brief description of the drawings]

【図１】本発明にかかる積層体の実施の形態をあらわす
断面図である。FIG. 1 is a sectional view showing an embodiment of a laminate according to the present invention.

【符号の説明】 １ 積層体 ２ 内層（ＰＶＤＦ層） ３ 外層（ＰＥ層） ４ 混合組成物層（接着層）[Description of Signs] 1 laminate 2 inner layer (PVDF layer) 3 outer layer (PE layer) 4 mixed composition layer (adhesive layer)

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】ポリエチレン系樹脂層と、ポリフッ化ビニ
リデン系樹脂層と、この両樹脂層の間に介在し、両樹脂
層を接着一体化する接着層とを備える積層体において、
前記接着層が、ポリメタクリル酸メチルをグラフト化し
たポリエチレンとポリメタクリル酸メチルとを含む混合
組成物で形成されていることを特徴とする積層体。1. A laminate comprising a polyethylene-based resin layer, a polyvinylidene fluoride-based resin layer, and an adhesive layer interposed between the two resin layers to bond and integrate the two resin layers.
A laminate, wherein the adhesive layer is formed of a mixed composition containing polyethylene grafted with poly (methyl methacrylate) and poly (methyl methacrylate). 【請求項２】接着層を形成する混合組成物中、ポリメタ
クリル酸メチルをグラフト化したポリエチレンとポリメ
タクリル酸メチルが、ポリメタクリル酸メチルをグラフ
ト化したポリエチレン中のポリメタクリル酸メチルを含
むポリメタクリル酸メチルの総和と、ポリメタクリル酸
メチルをグラフト化したポリエチレン中のボリエチレン
との重量比で、ポリメタクリル酸メチルの総和／ポリエ
チレン＝３５／６５〜９０／１０の割合で混合されてい
る請求項１に記載の積層体。2. A mixed composition for forming an adhesive layer, wherein polyethylene and polymethyl methacrylate grafted with polymethyl methacrylate are polymethacryl containing polymethyl methacrylate in polyethylene grafted with polymethyl methacrylate. 2. A mixture in a ratio of the sum of polymethyl methacrylate / polyethylene = 35/65 to 90/10 by weight ratio of the sum of methyl methacrylate and polyethylene in polyethylene grafted with polymethyl methacrylate. The laminate according to item 1. 【請求項３】ポリエチレン系樹脂層が外層となり、ポリ
フッ化ビニリデン系樹脂層が内層となる管状に成形され
ている請求項１または請求項２に記載の積層体。3. The laminate according to claim 1, wherein the polyethylene resin layer is an outer layer, and the polyvinylidene fluoride resin layer is an inner layer.