JPH10128884A - Fuel container and fuel pipe - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fuel container and a fuel pipe which are excellent in gasoline barrier properties, especially in oxygen-containing gasoline barrier properties, and are also excellent in impact resistance. SOLUTION: An ethylene-vinyl ester copolymer saponified product having an ethylene content of 20 to 60 mol% and a saponification degree of 90% or more, 60 to 99 wt%, and a (meth) acrylic acid content of 1
To provide a fuel container or a fuel pipe comprising a multilayer structure having a resin composition layer composed of 40 to 1% by weight of an ethylene- (meth) acrylic acid copolymer of 30 to 30% by weight.
Here, the ratio (A) / (B) of MI (A) of the saponified ethylene-vinyl ester copolymer to MI (B) of the ethylene- (meth) acrylic acid copolymer is 0.1 to 5.0. It is preferred that Further, it is preferable that the resin composition layer and the high-density polyethylene layer are laminated via an adhesive resin layer, or that the resin composition layer and the polyamide resin layer are laminated. In addition, it is more effectively achieved when the fuel container or the fuel pipe is used for oxygenated gasoline.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fuel container and a fuel pipe which are excellent in permeation performance (gasoline barrier property) and impact resistance to automobile fuel.

[0002]

2. Description of the Related Art As a plastic fuel tank, a polyethylene single-layer type fuel tank is widely used, but has a drawback that it has a relatively high gasoline permeability. On the other hand, gasoline barrier properties have been improved by subjecting polyethylene tanks to sulfone treatment (JP-B-46-23914) or chlorofluorocarbon treatment (JP-B-47-21877, JP-B-53-15862). A method of improving the content, or a method of mixing a substance having a barrier property such as nylon into polyethylene (Japanese Patent Application Laid-Open No. 4-296331).
Has been taken. There has also been proposed a three-type five-layer structure in which a tank has a multilayer structure, a nylon is used for a barrier layer, and a high-density polyethylene layer is provided on both sides of the tank via an adhesive resin layer.

On the other hand, from the viewpoint of strengthening regulations on environmental pollution in recent years, and preventing air pollution and saving gasoline consumption, methanol, methanol and the like have been used to improve the octane number of gasoline and reduce the amount of unburned hydrocarbons in exhaust gas. ethanol,
Gasoline blended with an oxygen-containing compound such as MTBE (hereinafter abbreviated as oxygen-containing gasoline) is used mainly in the United States.

However, in the above-described method of forming a multilayer structure of polyethylene and nylon, and in the method of mixing and extruding nylon with polyethylene and simultaneously dispersing the nylon in a discontinuous thin layer in the polyethylene layer, etc. There is a problem with the barrier property against oxygenated gasoline.
In addition, the method of sulfone-treating or fluorine-treating a single polyethylene layer has a problem of insufficient barrier properties against oxygen-containing gasoline.

[0005] Under such circumstances, a multilayer tank of polyethylene and a saponified ethylene-vinyl ester copolymer (hereinafter abbreviated as EVOH) has been proposed as a container having excellent gasoline barrier properties, and is more favorable than the above-mentioned various fuel containers. It has become possible to obtain a good gasoline barrier property. However, the multilayer tank has a problem in impact resistance.

In order to improve various problems of a fuel container having an EVOH resin as an intermediate layer, blending a polyolefin or a polyamide with the EVOH resin (Japanese Patent Laid-Open No. 6-2)
18891 and JP-A-7-52333) have also been proposed, but the gasoline barrier properties are greatly reduced and the melt stability is problematic. It is.

Further, a fuel pipe comprising a layer made of an EVOH resin or a composition mainly composed of an EVOH resin and a polyamide layer (Japanese Patent Publication No. 4-55392, Japanese Patent Application Laid-Open No. 7-52333) has been proposed. At present, there is no one that sufficiently satisfies both gasoline barrier properties and impact resistance.

[0008]

[Problems to be solved by the present invention] In view of this situation,
It is of great significance to provide a fuel container and a fuel pipe having good gasoline barrier properties and excellent impact resistance. Thus, the present invention provides a gasoline barrier property, particularly an oxygen-containing gasoline barrier property, by studying the composition of a resin composition containing EVOH as a main component.
Moreover, an object of the present invention is to provide a fuel container and a fuel tank which are excellent in impact resistance. As a result, not only is it adapted to environmental issues, but also the safety in actual use is greatly enhanced.

[0009]

The object of the present invention is to provide an ethylene copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of 90% or more.
Ethylene having a saponified vinyl ester copolymer content of 60 to 99% by weight and a (meth) acrylic acid content of 1 to 30% by weight.
This is achieved by providing a fuel container or a fuel pipe having a multilayer structure having a resin composition layer composed of 40 to 1% by weight of a (meth) acrylic acid copolymer. Here, MI of saponified ethylene-vinyl ester copolymer
MI of (A) and ethylene- (meth) acrylic acid copolymer
It is preferable that the ratio (A) / (B) of (B) is 0.1 to 5.0.

The above object is also effective when the resin composition layer and the high-density polyethylene layer are laminated via an adhesive resin layer, or when the resin composition layer and the polyamide resin layer are laminated. Is achieved. In addition, it is more effectively achieved when the fuel container or the fuel pipe is used for oxygenated gasoline.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, EVOH is obtained by saponifying an ethylene-vinyl ester copolymer and has an ethylene content of 20 to 60 mol%. If the ethylene content is less than 20 mol%, melt moldability is poor, and gasoline barrier properties under high humidity may be deteriorated. It is more preferably at least 25 mol%, and most preferably at least 30 mol%. On the other hand, if the ethylene content exceeds 60 mol%, the gasoline barrier properties deteriorate. More preferably 50 mol%
The content is more preferably 40 mol% or less.

As the vinyl ester, a typical example is vinyl acetate. Other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.)
Can also be used.

Further, a small amount of another monomer can be copolymerized with EVOH within a range not to impair the object of the present invention. Examples of monomers that can be copolymerized include α-olefins such as propylene, butene, isobutene, 4-methylpentene-1, hexene, and octene; and unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, and maleic anhydride. Examples thereof include acids, salts thereof, partial or complete esters thereof, nitriles thereof, amides thereof, anhydrides thereof, vinylsilane compounds such as vinyltrimethoxysilane, unsaturated sulfonic acids, salts thereof, alkylthiols, and vinylpyrrolidone.

In particular, when EVOH contains 0.0002 to 0.2 mol% of a vinylsilane compound as a copolymerization component, the consistency of the melt viscosity with the base resin at the time of coextrusion is improved, and a homogeneous copolymer is obtained. In addition to being extrudable, the dispersibility when EVOHs are used in a blend is improved, which is effective in improving moldability and the like. here,
Examples of the vinylsilane-based compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used.

[0015] The phosphorus compound concentration in the EVOH of the present invention is:
1 to 200 ppm, preferably 2 to 1 ppm in terms of phosphorus element weight
It is preferably from 50 ppm, most preferably from 5 to 100 ppm, from the viewpoint of moldability and thermal stability.

The addition of 10 to 500 ppm of alkali metal ions such as sodium ion, potassium ion and lithium ion to EVOH in terms of metal weight also enhances the effects of the present invention and improves the interlayer adhesion and compatibility. It is effective for Examples of the alkali metal compound include an aliphatic carboxylate, an aromatic carboxylate, a phosphate, and a metal complex of a monovalent metal. Specific examples thereof include sodium acetate, potassium acetate, sodium phosphate, and phosphoric acid. Lithium, sodium stearate, potassium stearate, sodium ethylenediaminetetraacetate and the like are preferred, and preferred are sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, and potassium stearate.

The EVOH used in the present invention preferably has a melt index (MI) (a value measured at 210 ° C. under a load of 2160 g) of preferably 0.1 to 50 g / 10.
Min, optimally between 0.5 and 20 g / 10 min. In the present invention, it may be more preferable to use one or more EVOHs having different ethylene contents and / or different degrees of saponification in a blend.

The ethylene- (meth) acrylic acid copolymer used in the present invention refers to a polymer having ethylene as a main component and copolymerizing acrylic acid or methacrylic acid. In the present invention, it does not include a so-called ionomer in which the carboxyl group in the copolymer exists in the form of a salt of a metal such as sodium or zinc. It is not clear why the object of the present invention is not achieved when such an ionomer is used, but it is as shown in Comparative Examples described later.

The (meth) acrylic acid content in the ethylene- (meth) acrylic acid copolymer is from 1 to 30% by weight,
It is preferably from 2 to 25% by weight, more preferably from 3 to 20% by weight.
% By weight. If the (meth) acrylic acid content is less than 1% by weight, the impact resistance may be deteriorated, possibly due to poor dispersion of the resin particles. If it exceeds 30% by weight, the thermal stability becomes poor.

The ethylene- (meth) used in the present invention
Suitable melt index of the acrylic acid copolymer (M
I) (value measured at 210 ° C. under a load of 2160 g) is
Preferably from 0.1 to 80 g / 10 min, optimally from 0.5 to 5
0 g / 10 minutes. In the present invention, the ethylene- (meth) acrylic acid copolymer may be used by blending two or more ethylene- (meth) acrylic acid copolymers having different (meth) acrylic acid contents and / or MIs. it can.

The content of EVOH in the resin composition of the present invention is 60 to 99% by weight, preferably 70 to 97% by weight, more preferably 80 to 95% by weight. The content of the ethylene- (meth) acrylic acid copolymer is 1 to 40.
%, Preferably 3 to 30% by weight, more preferably 5 to 20% by weight. When the blending ratio of the ethylene- (meth) acrylic acid copolymer is less than 1% by weight, the impact resistance of the molded product is reduced. If the blending ratio of the ethylene- (meth) acrylic acid copolymer exceeds 40% by weight, the gasoline barrier properties are significantly reduced.

Melt index (MI) of EVOH and ethylene- (meth) acrylic acid copolymer used in the present invention
(Value measured at 210 ° C. under a load of 2160 g) As a ratio, the ratio (A) / (B) of MI (A) of EVOH to MI (B) of ethylene- (meth) acrylic acid copolymer is 0.1%. 1
~ 5.0, more preferably 0.15
~ 3.0, optimally 0.2-2.0. By combining resins having MI ratios in such a range, the resin can be well dispersed and the object of the present invention can be achieved.

The resin composition of the present invention contains a hydrotalcite-based compound, a hindered phenol-based, a hindered amine-based heat stabilizer, a higher aliphatic acid, in order to enhance the effects of the present invention and to improve the melt stability and the like. It is preferable to add one or more metal salts of carboxylic acids (for example, calcium stearate, magnesium stearate, etc.) to the resin composition in an amount of 0.01 to 1% by weight.

Various additives can be added to the resin composition of the present invention, if necessary. Examples of such additives include antioxidants, plasticizers, heat stabilizers, ultraviolet absorbers, antistatic agents, lubricants, colorants, fillers, or other high molecular compounds, and Blends can be blended as long as the effects of the present invention are not impaired. Specific examples of the additives include the following.

Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2,2 '-Methylene-bis- (4-methyl-6-
t-butylphenol), octadecyl-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-t-butylphenol) and the like.

UV absorber: ethylene-2-cyano-
3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5 '-Methylphenyl) 5-
Chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like.

Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester and the like. Antistatic agents: pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins,
Polyethylene oxide, carbowax, etc. Lubricants: ethylene bis stearamide, butyl stearate and the like. Colorants: carbon black, phthalocyanine, quinacridone, indoline, azo pigments, red iron, etc. Filler: glass fiber, asbestos, ballastonite, calcium silicate, etc.

Many other high molecular compounds can be blended to such an extent that the effects of the present invention are not impaired.

The lamination structure of the laminated structure having the resin composition layer is not particularly limited, but it is possible to laminate the resin composition layer and the high-density polyethylene layer via an adhesive resin layer. preferable. This is because the gasoline barrier property under high humidity and the strength and the like are improved as compared with the case where the resin composition is used as a single layer. This configuration is particularly suitable for use as a fuel container.

The high-density polyethylene in the present invention is:
For example, it is obtained by using a Ziegler catalyst under high or medium pressure and has a density of 0.941 to 0.965 g / c.
m ³ , preferably 0.945 to 0.96 g / cm ³ . In the present invention, a preferable melt index (MI) of the high-density polyethylene is (210 ° C., 2160
g measured under a load) of 0.001 to 0.5 g / 1.
0 minutes, preferably 0.005 to 0.1 g / 10 minutes.

By laminating such a high-density polyethylene layer on the inner layer or the inner and outer layers of the resin composition layer, as shown in Examples described later, gasoline barrier properties are excellent.
Moreover, a fuel container and a fuel pipe having excellent impact resistance can be obtained. Although the high-density polyethylene layer is preferably in the innermost layer, or the innermost layer-outermost layer,
Laminating another resin layer on the innermost layer or the innermost layer-the outermost layer is free as long as the object of the present invention is not hindered. Further, it is free to mix another resin or the like in the high-density polyethylene layer as long as the object of the present invention is not hindered. Therefore, if the high-density polyethylene is the main component, the recovered layer described later is also considered as the high-density polyethylene layer in the present invention.

The resin used for the adhesive resin layer is not particularly limited, but may be a polyurethane-based or polyester-based one-pack or two-pack curable adhesive, an unsaturated carboxylic acid or an anhydride thereof (anhydrous anhydride). Maleic acid, etc.) to an olefin polymer or copolymer [polyethylene @ low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (SLDP)
E)｝, ethylene-vinyl acetate copolymer, ethylene-
(Meth) acrylic acid ester (methyl ester or ethyl ester) copolymer] is preferably used. By providing such an adhesive resin layer, it is possible to obtain a fuel tank and a fuel pipe which are excellent in interlayer adhesiveness and which are excellent in barrier properties and impact resistance which are the objects of the present invention.

Further, it is more preferable that the adhesive resin is a carboxylic acid-modified polyethylene resin from the viewpoint of adhesiveness with a high-density polyethylene resin or a polyamide resin or compatibility at the time of scrap recovery. Examples of such a carboxylic acid-modified polyethylene resin include polyethylene {low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (SLDPE)}, ethylene-vinyl acetate copolymer, ethylene- Carboxylic acid-modified (meth) acrylic ester (methyl ester or ethyl ester) copolymers and the like can be mentioned.

Another preferred structure of the laminated structure including the resin composition layer includes a resin composition layer laminated with a polyamide resin layer. This is because the strength, rigidity and the like can be improved as compared with the case where the resin composition is used in a single layer, and this is particularly effective when used as a fuel pipe.

The polyamide resin used for the polyamide resin layer is not particularly limited. Examples thereof include polycaproamide (nylon-6), polyundecaneamide (nylon-11), polylauryl lactam (nylon-12), and polylauryl lactam (nylon-12). Hexamethylene adipamide (nylon-
6,6), polyhexamethylene sebacamide (nylon-
6,12), caprolactam / lauryl lactam copolymer (nylon-6 / 12), caprolactam / aminoundecanoic acid copolymer (nylon-6 /
11), caprolactam / ω-aminononanoic acid copolymer (nylon-6 / 9), caprolactam / hexamethylenediammonium adipate copolymer (nylon-6 /
6,6) and copolymers such as caprolactam / hexamethylenediammonium adipate / hexamethylenediammonium sebacate copolymer (nylon-6 / 6,6 / 6,12). These polyamide resins can be used alone or in combination of two or more.

In the present invention, a scrap collected layer can be provided as needed. Here, as the scrap collected product, a molding loss portion generated when manufacturing a molded product such as a hollow container, a tubular container, and a tubular body, and a crushed product of the scrap collected product after being used by general consumers, and the like. is there. Also, scrap can be mixed with a high-density polyethylene layer or a polyamide layer.

In the present invention, the high-density polyethylene layer
E, the adhesive resin layer is AD, and the resin composition layer composed of EVOH and ethylene- (meth) acrylic acid copolymer is EVO.
When H and the scrap recovered material layer are represented by REG, the following layer configuration is a typical example.

3 layers: EVOH / AD / PE; 4 layers: EVOH / AD / REG / PE, EVOH / AD
/ PE / REG; 5 layers: PE / AD / EVOH / AD / PE, REG / A
D / EVOH / AD / PE, PE / AD / EVOH / A
D / REG; 6 layers: PE / REG / AD / EVOH / AD / PE, R
EG / PE / AD / EVOH / AD / PE, PE / RE
G / AD / EVOH / AD / REG, REG / PE / A
D / EVOH / AD / REG; 7 layers: PE / REG / AD / EVOH / AD / REG /
PE, PE / REG / AD / EVOH / AD / PE / R
EG, REG / PE / AD / EVOH / AD / PE / R
EG, REG / PE / AD / EVOH / AD / REG /
PE; however, the layer configuration is not limited to the above. Among these, a preferred layer configuration is EVOH / AD /
PE, PE / AD / EVOH / AD / PE, PE / RE
G / AD / EVOH / AD / PE etc. are shown.

When a resin composition layer composed of EVOH and an ethylene- (meth) acrylic acid copolymer is laminated on a polyamide resin layer, the polyamide layer may be replaced with a polyamide layer instead of the high-density polyethylene layer. And various configurations using. In this case, unlike the case where a high-density polyethylene layer is used, EVOH and ethylene-
The adhesive resin layer between the resin composition layer composed of the (meth) acrylic acid copolymer and the polyamide resin layer may or may not be provided.

Although the thickness of each of these layers is not particularly limited, the preferred thickness for use as a fuel container is a high-density polyethylene layer or a polyamide layer 300.
0-10000μ, more preferably 4000-6000
μ, adhesive resin layer 20 to 1000 μ, more preferably 50
The composition layer is composed of EVOH and an ethylene- (meth) acrylic acid copolymer, and has a thickness of 5 to 1000 µ, more preferably 60 to 800 µ. The total thickness is 3000-1
0000μ, more preferably 4000-7000μ. These thicknesses refer to the thickness of the body of the fuel tank. Further, a suitable thickness when used as a fuel pipe must be appropriately adjusted according to the diameter of the pipe, but a preferable thickness ratio of each layer is the same as that of the fuel container.

In the present invention, various additives can be blended in each layer forming the multilayer structure. Such additives include antioxidants, plasticizers, heat stabilizers,
Examples thereof include an ultraviolet absorber, an antistatic agent, a lubricant, a coloring agent, a filler, and the like, and specifically, those described above as those that can be added to the composition layer.

The method for obtaining the fuel container and the fuel pipe having the multilayer structure of the present invention is not particularly limited. For example, molding methods used in the field of general polyolefins, such as extrusion molding, Stamping molding, blow molding, injection molding and the like can be mentioned, and a co-extrusion pipe molding method and a co-extrusion blow molding method are particularly preferable.

The fuel container according to the present invention is a fuel container mounted on an automobile, a motorcycle, a ship, an aircraft, a generator, industrial or agricultural equipment, or a portable container for refueling these fuel containers. And also a container for storing the fuel used to operate them. The fuel pipe means a pipe attached to the fuel container or a pipe independent of the fuel container.
Typical examples of the fuel include regular gasoline, gasoline blended with methanol or MTBE, and other heavy oils, light oils, and kerosene. Among them, the fuel container or fuel pipe of the present invention is:
This is particularly effective for gasoline blended with methanol and / or MTBE.

[0044]

EXAMPLES Examples and comparative examples are shown below. Example 1 Sodium acetate was 65 pp in terms of sodium element weight.
m, EVOH containing a phosphorus compound in the form of a phosphate in an amount of 100 ppm by weight per phosphorus atom, an ethylene content of 32 mol%, a saponification degree of 99.6%, and MI = 3.1 g / 10 min (2
10 ° C, 2160g load) 90% by weight and ethylene
(Meth) acrylic acid copolymer (hereinafter abbreviated as EMAA)
含量 Methacrylic acid copolymer content: 9 mol%, Mitsui Dupont Chemical “Nucrel 0903HC, MI = 5.7 g /
After 10 minutes (210 ° C., 2160 g load)｝ 10% by weight, the mixture was melt-kneaded at a cylinder temperature of 210 ° C. using a 30 mmφ twin screw extruder to form pellets.

Using these pellets as an intermediate layer, high-density polyethylene (HDPE) @ MI = 0.025 g / 10 min (2
10 ° C., 2160 g load), density 0.96 g / cm ³ ,
“HZ8200B” manufactured by Mitsui Petrochemical Co., Ltd. was used as the outer layer, and the adhesive resin layer (AD) was further modified with maleic anhydride-modified polyethylene {MI = 1.8 g / 10 min (210 ° C., 216
0g load), 3 types and 5 layers (inner HDP) by co-extrusion blow molding using Mitsui Petrochemical "Admer GT4"
E / AD / resin composition / AD / outer layer HDPE = 1163
/ 50/75/50 / 1163μ) was obtained.

As a test for gasoline barrier properties, 300 cc of model gasoline (A) [gasoline {common petroleum: unleaded regular} (85 vol%) mixed with methanol (15 vol%)] was poured into this multilayer container and completely leaked. Make sure that there is no explosion-proof constant temperature and high humidity layer (20 ° C-65% R
H), and the amount of weight loss after 4 days was measured (n
= 6 average). Next, as an impact resistance test, the multilayer container was filled with water, dropped on concrete, and the drop height at which the bottle was destroyed (water inside the container leaked) was determined. For the breaking height, a 50% breaking height was determined by using the calculation method shown in the JIS test method (part of “8. Calculation” of K7211) using the test result of n = 30. Table 1 shows the measurement results of these barrier properties and impact resistance.

Comparative Example 1 A sample was prepared and tested in the same manner as in Example 1 except that the same EVOH resin used in Example 1 was used alone instead of the resin composition layer. I did it. Table 1 summarizes the evaluation results of the obtained multilayer containers.

Examples 2 and 3, Comparative Example 2 The same EVOH and EMA used in Example 1
A, using a mixing ratio of 95% by weight of EVOH, EMAA
5% by weight (Example 2), 80% by weight of EVOH, EMAA
20% by weight (Example 3), 50% by weight of EVOH, EMA
Example 1 except that A was changed to 50% by weight (Comparative Example 2).
In the same manner, a sample was prepared and tested. Table 1 summarizes the evaluation results of the obtained multilayer containers.

Examples 4 and 5 EVOH used in Example 1 was obtained by mixing EVOH having different ethylene contents with an ethylene content of 27 mol% and a saponification degree of 99.6.
%, MI = 3.9 g / 10 min (210 ° C., 2160 g load) (Example 4), {ethylene amount 44 mol%, saponification degree 99.7%, MI = 3.5 g / 10 min (210 ° C.) , 2
A sample was prepared and tested in the same manner as in Example 1, except that the load was changed to 160 g load) (Example 5).
Table 1 summarizes the evaluation results of the obtained multilayer containers.

Examples 6-8, Comparative Examples 3-7 EMAA used in Example 1 Methacrylic acid content: 9% by weight, Mitsui Dupont Chemical "Nucrel 09"
03HC, MI = 5.7 g / 10 min (210 ° C., 216
A sample was prepared and tested in the same manner as in Example 1 except that the following resin was used instead of (0 g load)｝. Table 1 summarizes the evaluation results of the obtained multilayer containers. Example 6: EMAA @ methacrylic acid content: 4% by weight,
Mitsui Dupont Chemical "Nucrel AN4214C",
MI = 12.2 g / 10 min (210 ° C., 2160 g load) Example 7; EMAA methacrylic acid content; 12% by weight, DuPont Mitsui Chemical “Nucrel 1207C”,
MI = 13.4 g / 10 min (210 ° C., 2160 g load)｝ Example 8: Ethylene-acrylic acid copolymer (hereinafter EAA)
Acrylic acid (AA) content: 9.0% by weight, Dow Chemical "Primacol 1430, MI = 8.
7 g / 10 min (210 ° C., 2160 g load) Comparative Example 3: Ethylene-methyl methacrylate copolymer ｛Methyl methacrylic acid (MMA) content: 18% by weight, Sumitomo Chemical “Aclift WH303, MI = 12.1”
g / 10 minutes (210 ° C., 2160 g load)｝ Comparative Example 4; maleic anhydride-modified polyethylene ｛MI =
3.6 g / 10 min (210 ° C., 2160 g load), “Admer NF500” manufactured by Mitsui Petrochemical Co., Ltd. 例 Comparative Example 5; Ionomer ｛Mitsui Dupont Chemical “Himilan 1652, MI = 7.6 g / 10 min (210 ° C.,
Comparative Example 6; LDPE “Milason B32 manufactured by Mitsui Petrochemical Co., Ltd.)
4, MI = 3.4 g / 10 min (210 ° C., 2160 g load) Comparative Example 7: Nylon {Nylon 6 (PA-6)} MI =
7.2 g / 10 min (230 ° C., 2160 g load), “UBE Nylon 1022B” manufactured by Ube Industries, Ltd.

Examples 9 and 10 Samples were prepared and tested in the same manner as in Example 1 except that the following EVOH and ethylene- (meth) acrylic acid copolymer were used in combination. At this time, by changing the MI of the EVOH and the ethylene- (meth) acrylic acid copolymer used, the ratio MI (A) / MI (B)
Was adjusted. Table 1 summarizes the evaluation results of the obtained multilayer containers. Example 9 EVOH ｛ethylene content 32 mol%, saponification degree 99.6
%, MI = 1.2 g / 10 min (210 ° C., 2160 g load), EMAA, methacrylic acid content: 9% by weight, DuPont Mitsui Chemical “Nucrel NC0908HG”,
MI = 15.3 g / 10 min (210 ° C., 2160 g load) Example 10 EVOH ethylene content 32 mol%, saponification degree 99.6
%, MI = 33.0 g / 10 min (210 ° C., 2160 g
Load)｝, EMAA ｛Methacrylic acid content: 9% by weight,
Mitsui Dupont Chemical "Nucrel 0903HC, MI
= 5.7g / 10min (210 ° C, 2160g load) 荷重

[0052]

[Table 1]

Example 11 In Example 1, the model gasoline (A) was replaced with the model gasoline (B) [gasoline {common petroleum: unleaded regular}.
(100% by volume)] and a gasoline barrier property test was performed in the same manner as in Example 1 except that the barrier measurement period was set to 6 months. As a result, the weight loss was 0.012 g.

Comparative Example 8 In Comparative Example 1, the model gasoline (A) was replaced with the model gasoline (B) [gasoline {common petroleum: unleaded regular}.
(100% by volume)] and a gasoline barrier property test was performed in the same manner as in Comparative Example 1 except that the barrier measurement period was changed to 6 months. As a result, the weight loss was 0.011 g.

Example 12 Using the same resin composition comprising EVOH and EMAA as in Example 1, the resin composition was applied to a co-extrusion multilayer pipe molding apparatus to produce a multilayer pipe. The configuration of the pipe is 12
Polyamide@MI=0.7 g / 10 min (210 ° C., 21
UBE nylon 303
5 "is 450 μm and the adhesive resin layer has a maleic anhydride-modified polyethylene {MI = 3.5 g / 10 min (210 ° C., 2
160 g), Mitsui Petrochemical "Admer VF50
0 "} is 50μ and further 6 polyamide layers {MI = 2.3
g / 10 minutes (230 ° C., 2160 g load), “Amilan CM1044” manufactured by Toray Co., Ltd. is 100 μm, the resin composition layer is 150 μm, and the innermost layer is “Amilan CM104 manufactured by Toray Co., Ltd.”
6 "250μ. The thus obtained four kinds and five layers of (outer layer 12 polyamide / adhesive resin layer / 6 polyamide / resin composition layer / inner layer 6 polyamide = 450/50/100 /
150/250 μ) A pipe having an outer diameter of 10 mm was obtained.

For the measurement of the barrier properties, the obtained pipe was cut into a length of 25 cm, both ends were plugged, 10 cc of the same model gasoline as in Example 1 was poured, and the weight loss after one month. Was measured. On the other hand, for the impact resistance test, a four-type, five-layer sheet having the same thickness and the same structure as the above-mentioned pipe was produced by the co-extrusion molding method.
At D3029 (−40 ° C.), impact resistance was measured as breaking energy. Table 2 shows the results of these barrier properties and impact resistance.

Comparative Example 9 Example 1 was repeated except that EVOH alone was used instead of the resin composition comprising EVOH and EMAA.
Obtain a multilayer pipe and a multilayer sheet under the same conditions as in 2,
A barrier test and an impact resistance test were performed. Table 2 shows the results of these tests.

[0058]

[Table 2]

[0059]

The fuel container and the fuel pipe of the present invention are:
It has excellent gasoline barrier properties, especially oxygen-containing gasoline barrier properties, and also has excellent impact resistance.

Claims (5)

[Claims] 1. A saponified ethylene-vinyl ester copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of 90% or more, 60 to 99% by weight, and a (meth) acrylic acid content of 1.
A fuel container or a fuel pipe comprising a multilayer structure having a resin composition layer comprising 40 to 1% by weight of an ethylene- (meth) acrylic acid copolymer of 30 to 30% by weight. 2. The ratio (A) / (B) of MI (A) of a saponified ethylene-vinyl ester copolymer to MI (B) of an ethylene- (meth) acrylic acid copolymer is 0.1-5. .0
The fuel container or the fuel pipe according to claim 1, wherein 3. The resin composition layer and the high-density polyethylene layer are laminated via an adhesive resin layer.
A fuel container or a fuel pipe according to claim 1. 4. The fuel container or fuel pipe according to claim 1, wherein a resin composition layer and a polyamide resin layer are laminated. 5. The fuel container or fuel pipe according to claim 1, which is for oxygenated gasoline.