JP2002052659A - Multilayered molded part for fuel container excellent in gasoline barrier properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a multilayered molded part for a fuel container excellent in gasoline barrier properties and mechanical strength. SOLUTION: The multilayered molded part for the fuel container consists of a barrier resin composition (A) layer, which consists of 60-95 wt.% of (a1) an ethylene/vinyl alcohol copolymer with an ethylene content of 5-60 mol% and a saponification value of 85% or more and 5-40 wt.% (a2) polymer particles having a multilayered structure, and a resin composition (B) layer which consists of 1-99 wt.% of at least one kind of a resin (b1) selected from the group consisting of a carboxylic acid modified polyolefin and a boric acid modified resin and 1-99 wt.% of a thermoplastic resin (b2) having a solubility parameter (calculated from formula of Fedors) of 11 or less other than (b1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer molded part for a fuel container having excellent gasoline barrier properties, heat sealability with a fuel tank and impact resistance, and a fuel in which the molded part is mounted on a fuel container body. For containers.

[0002]

2. Description of the Related Art In recent years, fuel tanks such as those used in automobiles have been put into practical use from metal to thermoplastic resin tanks in view of weight reduction, rust prevention, easy molding processability, and recyclability. It is being actively promoted.

However, when a tank made of a thermoplastic resin is used, the permeation and volatilization of gasoline components from the tank is a problem, so that an ethylene-vinyl alcohol copolymer (hereinafter referred to as EVOH) having a high gasoline barrier property is used.
(May be abbreviated as ")" has been developed (Japanese Patent Laid-Open No. 9-29904). By including EVOH in the fuel container as described above, the permeation and volatilization of gasoline components from the fuel container main body is greatly improved.

On the other hand, molded parts attached to the fuel container (for example, a fuel tube, a gas vent line of a filler port, a valve for depressurizing, and a connector to these container bodies)
Is generally made of high-density polyethylene. Therefore, the fuel permeates and volatilizes. Therefore, even if the fuel container body has excellent gas barrier properties, the fuel permeates and volatilizes from the molded parts to be connected, and the amount thereof is not negligible.

For this reason, it is conceivable to use a barrier resin (for example, EVOH) instead of high-density polyethylene. However, when the barrier resin alone is used as a molded part for a fuel container, the problem of gasoline permeation and volatilization can be solved, but the heat-fusibility with the fuel container body and impact resistance are unsatisfactory. Becomes

[0006]

Therefore, there is a need for a molded part for a fuel container that exhibits excellent performance in gasoline barrier properties, heat fusion with a fuel tank, and impact resistance.
In a fuel container equipped with such a molded part, leakage of fuel from a connector portion connecting a fuel tube, a gas vent line of a filler port, a pressure release valve, and the like to a fuel container main body is greatly improved.

[0007]

According to the present invention, there are provided an ethylene-vinyl alcohol copolymer (a1) having an ethylene content of 5 to 60 mol% and a saponification degree of 85% or more, 60 to 95% by weight, and a multi-layered polymer particle. (A2) a barrier resin composition (A) layer consisting of 5 to 40% by weight, and 1 to 99% by weight of at least one resin (b1) selected from the group consisting of a carboxylic acid-modified polyolefin and a boronic acid-modified resin; And a resin composition (B) layer comprising 1 to 99% by weight of a thermoplastic resin (b2) having a solubility parameter of 11 or less (calculated from the Fedors equation) other than (b1). Related to parts.

[0008] In a preferred embodiment, the thermoplastic resin (b2) is a polyolefin resin, more preferably high density polyethylene.

In a preferred embodiment, the barrier resin composition (A) layer and / or the resin composition (B) layer contains 1 to 50% by weight of an inorganic filler.

In a preferred embodiment, the molded part is molded by a multilayer injection molding machine. In a more preferred embodiment, the molded part is molded by an insert injection molding machine, a two-color molding machine or a co-injection molding machine.

In a preferred embodiment, the molded part is at least one member selected from the group consisting of a fuel container connector, a fuel container cap, and a fuel container valve.
Is a seed.

In a preferred embodiment, the molded part is mounted on a fuel container body via a resin composition (B) layer. In another preferred embodiment, the molded part is attached to the fuel container body by heat fusion. In a particularly preferred embodiment, the fuel container provided with the multilayer molded part of the present invention is used as a gasoline tank for automobiles.

It is also preferable that a component made of the thermosetting resin (C) is mounted on the fuel container body via the multi-layer molded component for a fuel container.

Further, it is preferable that the thermosetting resin (C) is a polymethylene oxide resin.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The multilayer molded part for a fuel container according to the present invention comprises an ethylene-vinyl alcohol copolymer (a1) 60 having an ethylene content of 5 to 60 mol% and a saponification degree of 85% or more.
To 95% by weight and multilayer polymer particles (a2) 5 to 4
0% by weight of a barrier resin composition (A) layer and at least one resin (b1) 1 to 1 selected from the group consisting of a carboxylic acid-modified polyolefin and a boronic acid-modified resin
The resin composition (B) layer comprises 99% by weight and 1 to 99% by weight of a thermoplastic resin (b2) having a solubility parameter (calculated from the Fedors equation) of 11 or less other than the above (b1).

The resin composition (B) has a multilayer structure composed of the barrier resin composition (A) layer and the resin composition (B) layer.
Heat-sealing property with the tank body of the layer, adhesion to the barrier resin composition (A) layer, good mechanical strength and gasoline barrier properties of the barrier resin composition (A) layer, organic solvent resistant It is possible to obtain a multi-layer molded part for a fuel container having both heat resistance and impact resistance.

The EVOH (a1) used in the present invention is preferably obtained by saponifying an ethylene-vinyl ester copolymer, and has an ethylene content of 5 to 60 mol%. The lower limit of the ethylene content is preferably at least 15 mol%, more preferably at least 20 mol%, and still more preferably at least 25 mol%. The upper limit of the ethylene content is preferably 55 mol% or less, more preferably 5 mol% or less.
0 mol% or less. If the ethylene content is less than 5 mol%, the melt moldability deteriorates. On the other hand, if it exceeds 60 mol%, the barrier properties become insufficient.

Further, the EVOH (a) used in the present invention
The saponification degree of the vinyl ester component of 1) is 85% or more. The degree of saponification of the vinyl ester component is preferably 90
% Or more, more preferably 95% or more, still more preferably 97% or more, and optimally 99% or more. If the degree of saponification is less than 85%, gasoline barrier properties,
Insufficient thermal stability.

A typical example of the vinyl ester used in the production of EVOH is vinyl acetate.
Other fatty acid vinyl esters (vinyl propionate,
Vinyl pivalate) can also be used. Also, EVOH
Is a vinyl silane compound as a copolymer component 0.0002 to
0.2 mol% can be contained. Here, as the vinylsilane-based compound, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β
-Methoxy-ethoxy) silane and γ-methacryloxypropylmethoxysilane. Among them, vinyltrimethoxysilane and vinyltriethoxysilane are preferably used. Further, other comonomer such as propylene, butylene, or unsaturated monomer such as (meth) acrylic acid, methyl (meth) acrylate or ethyl (meth) acrylate, as long as the object of the present invention is not hindered. A carboxylic acid or an ester thereof and vinylpyrrolidone such as N-vinylpyrrolidone can also be copolymerized.

Further, a boron compound may be blended with EVOH (a1) within a range not to impair the object of the present invention. Here, examples of the boron compound include boric acids, borate esters, borates, borohydrides, and the like. Specifically, examples of boric acids include orthoboric acid, metaboric acid, tetraboric acid, and the like.Examples of borate esters include triethyl borate, trimethyl borate, and the like. Examples include alkali metal salts, alkaline earth metal salts of acids, borax, and the like. Of these compounds, orthoboric acid is preferred.
When the boron compound is blended, the content of the boron compound is preferably 20 to 2000 pp in terms of boron element.
m, more preferably 50 to 1000 ppm. When the content of the boron compound is in such a range, EVOH with suppressed torque fluctuation during heating and melting can be obtained. If it is less than 20 ppm, the effect of improving the suppression of torque fluctuation during heating and melting may be reduced, and if it exceeds 2000 ppm, gelation is likely to occur, resulting in poor moldability.

The EVOH (a) used in the present invention
Contrary to 1), it is also preferable to contain an alkali metal salt in an amount of 5 to 5000 ppm in terms of an alkali metal element, because it is effective for improving interlayer adhesion and the like. A more preferable content of the alkali metal salt is 20 in terms of an alkali metal element.
１０００1000 ppm, more preferably 30-500 ppm. Here, examples of the alkali metal include lithium, sodium, and potassium, and examples of the alkali metal salt include a monovalent metal aliphatic carboxylate, an aromatic carboxylate, a phosphate, and a metal complex. For example, sodium acetate, potassium acetate, sodium phosphate, lithium phosphate, sodium stearate, potassium stearate,
And sodium salts of ethylenediaminetetraacetic acid. Among them, sodium acetate, potassium acetate and sodium phosphate are preferred.

The EVOH (a) used in the present invention
In contrast to 1), the phosphoric acid compound is converted to a phosphoric acid radical in an amount of 20 to 5
It is also preferable that the content is 00 ppm, more preferably 30 to 300 ppm, and most preferably 50 to 200 ppm. By mixing the phosphoric acid compound in the above range, EVOH
The thermal stability of (a1) can be improved. In particular, it is possible to suppress the occurrence and coloring of gel-like bumps when performing melt molding for a long time.

The type of the phosphoric acid compound to be incorporated into the EVOH (a1) is not particularly limited. Various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. The phosphate may be contained in any form of a first phosphate, a second phosphate, and a third phosphate, and the cationic species thereof is not particularly limited. ,
It is preferably an alkaline earth metal salt. Among them, it is preferable to add a phosphorus compound in the form of sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate.

The preferred melt flow rate (MFR) of the EVOH (a1) used in the present invention (190 ° C., 216
(Under 0 g load) is 0.1 to 50 g / 10 min, more preferably 0.3 to 40 g / 10 min, and even more preferably 0.5 to 30 g.
/ 10 minutes. However, the melting point is around 190 ° C or 1
Those exceeding 90 ° C. were measured at a plurality of temperatures equal to or higher than the melting point under a load of 2160 g, and the reciprocal of the absolute temperature was plotted on the abscissa and the logarithm of MFR was plotted on the ordinate in a semilogarithmic graph. Represent. These EVOH resins (a1) can be used alone or in combination of two or more.

In addition, a heat stabilizer, an ultraviolet absorber, an antioxidant, a colorant, other resins (polyamide, polyolefin, etc.), and a plasticizer such as glycerin or glycerin monostearate may be used within a range not to impair the object of the present invention. EVOH (a
It can also be blended in 1). The addition of a metal salt of a higher aliphatic carboxylic acid or a hydrotalcite compound is effective from the viewpoint of preventing the EVOH (a1) from being deteriorated by heat.

Here, as the hydrotalcite compound, in particular, M _x Al _y (OH) _{2x + 3y− 2z} (A) _z · aH ₂ O
(M is Mg, Ca or Zn, A is CO ₃ or HP
O ₄ , x, y, z, and a are positive numbers). Particularly preferred examples include the following hydrotalcite compounds.

[0027] _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O Mg 8 Al 2 (OH) 20 CO 3 · 5H 2 O Mg 5 Al 2 (OH) 14 CO 3 · 4H 2 O Mg 10 Al 2 ( _{OH) 22 (CO 3) 2} · 4H 2 O Mg 6 Al 2 (OH) 16 HPO 4 · 4H 2 O Ca 6 Al 2 (OH) 16 CO 3 · 4H 2 O Zn 6 Al 6 (OH) 16 CO 3 _{· 4H 2 O Mg 4. 5} Al 2 (OH) 13 CO 3 · 3.5H 2 O

Further, as the hydrotalcite compound,
JP-A-1-308439 (US Pat. No. 4,954,557)
The hydrotalcite-based solid solution described,
[Mg _0.75Zn_0.25]_0.67Al_0.33(OH)_Two(CO_Three)
_0.167・ 0.45H_TwoSomething like O can also be used
You.

The metal salt of a higher aliphatic carboxylic acid is a metal salt of a higher fatty acid having 8 to 22 carbon atoms. 8 to 2 carbon atoms
2 higher fatty acids include lauric acid, stearic acid,
And myristic acid. Examples of the metal include sodium, potassium, magnesium, calcium, zinc, barium, aluminum and the like. Of these, alkaline earth metals such as magnesium, calcium and barium are preferred.

Metal salts of these higher aliphatic carboxylic acids,
Alternatively, the content of the hydrotalcite compound is EVOH
(A1) 0.01 to 3 parts by weight, preferably 0.05 to 2.5 parts by weight, per 100 parts by weight.

The multilayer polymer particles (a2) used in the present invention are particles having at least a hard layer and a rubber layer. Either layer may be the outermost layer, but it is preferable to have a hard layer as the outermost layer and a rubber layer inside. Here, the rubber layer means a polymer layer having a glass transition temperature (hereinafter, sometimes referred to as Tg) of 25 ° C. or lower, and the hard layer means a polymer layer having a Tg higher than 25 ° C. The multilayer polymer particles may be composed of two layers, may be composed of three layers, or may be composed of four or more layers. Rubber layer (center layer) for two-layer structure
/ Hard layer (outermost layer). In the case of a three-layer structure,
Hard layer (center layer) / rubber layer (middle layer) / hard layer (outermost layer), rubber layer (center layer) / rubber layer (middle layer) / hard layer (outermost layer) or rubber layer (center layer) / hard Layer (middle layer)
/ In the case of a four-layer structure, for example, a rubber layer (center layer) / hard layer (intermediate layer) / rubber layer (intermediate layer) / hard layer (outermost layer) Configuration.

The composition of the rubber layer of the multi-layer polymer particles (a2) used in the present invention is not particularly limited. Examples of preferable polymers for constituting the rubber layer include polybutadiene, polyisoprene, and butadiene-isoprene. Copolymers, polychloroprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylate-butadiene copolymer and other conjugated diene-based polymers, hydrogenated conjugated diene-based polymers, ethylene- Olefin rubbers such as propylene copolymers,
Examples include acrylic rubbers such as polyacrylates, polyorganosiloxanes, thermoplastic elastomers, ethylene ionomer copolymers, and the like, and one or more of these are used. Among them, acrylic rubber,
A conjugated diene polymer or a hydrogenated product of a conjugated diene polymer is preferred.

The acrylic rubber is formed by polymerizing an acrylic ester. As acrylic acid esters,
Examples include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and the like. Among them, butyl acrylate or ethyl acrylate is preferred.

The acrylic rubber or the conjugated diene polymer is produced mainly by polymerizing a monomer system composed of an alkyl acrylate and / or a conjugated diene compound. The acrylic rubber or the conjugated diene-based polymer can be obtained by copolymerizing another monofunctional polymerizable monomer in addition to the above monomer, if necessary. Other monofunctional monomers that can be copolymerized include methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate, naphthyl methacrylate, Methacrylic esters such as isobornyl methacrylate; aromatic vinyl compounds such as styrene and α-methylstyrene; and acrylonitrile. The content of the other monofunctional polymerizable monomer is desirably 20% by weight or less of the entire polymerizable monomer forming the rubber layer.

The rubber layer forming a part of the multi-layer polymer particles (a2) used in the present invention preferably has a crosslinked molecular chain structure for exhibiting rubber elasticity. It is preferable that the molecular chains of the layer and the molecular chains in the layer adjacent thereto are grafted by a chemical bond. For that purpose, in the monomer polymerization for forming the rubber layer, it may be preferable to use a small amount of a polyfunctional polymerizable monomer in combination as a crosslinking agent or a grafting agent.

The polyfunctional polymerizable monomer has carbon-
Monomers having two or more carbon-carbon double bonds, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, and cinnamic acid and unsaturated alcohols such as allyl alcohol and methallyl alcohol; Esters with glycols such as ethylene glycol and butanediol; esters of the above-mentioned unsaturated alcohols with dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and maleic acid. Specific examples of polyfunctional polymerizable monomers include allyl acrylate, methallyl acrylate, allyl methacrylate,
Methallyl methacrylate, allyl cinnamate, methallyl cinnamate, diallyl maleate, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, divinylbenzene, ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate G, hexane geo-
Luge (meth) acrylate and the like are exemplified. The term “di (meth) acrylate” is used for “diacrylate”.
G "and" dimethacrylate ". These may be used alone or in combination of two or more. Among them, allyl methacrylate is preferably used.

The amount of the polyfunctional polymerizable monomer used is preferably limited to 10% by weight or less of the entire polymerizable monomer forming the rubber layer. This is because if the amount of the polyfunctional polymerizable monomer is too large, it is considered that the performance as a rubber is reduced, and the flexibility of the thermoplastic resin composition is reduced. When a monomer system containing a conjugated diene-based compound as a main component is used, it itself does not function as a crosslinking or graft point, and therefore, it is not always necessary to use a polyfunctional polymerizable polymer.

Examples of the radical polymerizable monomer that can be used for forming the hard layer in the present invention include, for example,
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; methacrylates having an alicyclic skeleton such as cyclohexyl methacrylate, isobornyl methacrylate, and adamantyl methacrylate; aromatic rings such as phenyl methacrylate A methacrylate having the following formula: styrene, α-
Aromatic vinyl compounds such as methylstyrene; acrylonitrile; These radically polymerizable monomers can be used alone or in combination of two or more. Preferred radical polymerizable monomer systems include methyl methacrylate or styrene alone or a combination of two or more radical polymerizable monomers containing the same as a main component.

In the present invention, when the multilayer polymer particles have at least one functional group having reactivity or affinity for a hydroxyl group, the dispersibility of the multilayer polymer particles in EVOH is improved, and The impact strength of the resulting barrier resin composition (A) layer is further improved. Therefore, in the polymerization reaction for producing the multilayer polymer particles, as a part of the monomer, a radical having a functional group having reactivity or affinity for a hydroxyl group or a functional group in a form in which it is protected. It is preferable to use a polymerizable compound.

The copolymerizable compound which is preferably used for forming the above-mentioned functional group of the multilayer polymer particles and has reactivity or affinity with a hydroxyl group includes a hydroxyl group in EVOH under the following mixing conditions. And an unsaturated compound having a group capable of forming a chemical bond by reacting with a group or a group capable of forming an intermolecular bond such as a hydrogen bond with a hydroxyl group. Examples of the functional group having reactivity or affinity for the hydroxyl group include, for example, an acid group such as a hydroxyl group, an epoxy group, an isocyanate group (—NCO), and a carboxyl group, and a group derived from maleic anhydride. Acid anhydride group, protective group is removed under the following mixing conditions,
Examples include groups that change to any of the groups described above.

Specific examples thereof include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl crotonate, 3-hydroxy-1-propene, and 4-hydroxy-1-butene. A polymerizable compound having a hydroxyl group, such as cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene;
Glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, 3,4-epoxybutene, 4,
5-epoxypentyl (meth) acrylate, 10,1
Epoxy group-containing polymerizable compounds such as 1-epoxyundecyl methacrylate and p-glycidylstyrene; acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid,
And carboxylic acids such as maleic acid, citraconic acid, aconitic acid, mesaconic acid and methylenemalonic acid. In addition,
The term “di (meth) acrylate” is a general term for “diacrylate” and “dimethacrylate”,
“(Meth) acrylic acid” means a general term for “acrylic acid” and “methacrylic acid”.

Among the above functional groups having reactivity or affinity for the hydroxyl group, an acid group such as a carboxyl group, an acid anhydride group derived from maleic anhydride, and an epoxy group are preferable. Among them, an acid group such as a carboxyl group or an epoxy group is particularly preferred. Examples of the acid group such as a carboxyl group include methacrylic acid and acrylic acid, and examples of the epoxy group include glycidyl methacrylate and glycidyl acrylate.

The amount of the functional group having a reactivity or affinity for a hydroxyl group or the radical polymerizable compound having a functional group in a protected form thereof depends on the amount of the monomer for producing the multilayer polymer particles. It is preferably from 0.01 to 75% by weight, more preferably from 0.1 to 40% by weight, based on the whole. The above-mentioned protecting group is a group which deviates under the mixing conditions with EVOH as described later and gives the functional group, and may be any group which does not inhibit the object of the present invention. Examples of the radical polymerizable compound having a protected functional group include t-butyl methacrylatecarbamate.

When the polymer particles having a multilayer structure have a functional group having reactivity or affinity for a hydroxyl group, this functional group is preferably present on the molecular chain in the outermost hard layer. . However, in the form of a resin composition with EVOH, each layer (outermost layer) of the polymer particles having a multilayer structure can be used as long as this functional group can substantially react with a hydroxyl group in EVOH or form an intermolecular bond. , An intermediate layer, or an inner layer).

The content of the rubber layer in the multilayer polymer particles is preferably in the range of 50 to 90% by weight. If the amount of the polymer portion forming the rubber layer is too small, the flexibility is insufficient, and if the amount of the polymer portion forming the outermost layer is too small, the handleability of the multilayer polymer particles is reduced.

The polymerization method for producing the multilayered polymer particles used in the present invention is not particularly limited. For example, spherical multilayered polymer particles can be easily prepared by following a usual emulsion polymerization method. Can be obtained. Emulsion polymerization is carried out according to a method commonly used by those skilled in the art, and a chain transfer agent such as octyl mercaptan and lauryl mercaptan can be used as necessary. After the emulsion polymerization, the multilayer polymer particles are separated from the polymer latex and obtained according to a method commonly used by those skilled in the art (for example, a method such as coagulation and drying).

At this time, there is no particular limitation on the average particle diameter of each of the obtained multilayer polymer particles. However, if the average particle diameter is too small, the handleability of the multilayer polymer particles decreases, and conversely, the average particle diameter decreases. If it is too much, the effect of improving the impact strength of the barrier resin (A) layer is reduced. Therefore, the average particle diameter of each multilayer polymer particle is preferably in the range of 0.02 to 2 μm, and more preferably in the range of 0.05 to 1.0 μm. The form of the multilayer polymer particles to be produced is not particularly limited, for example, pellets, powders, or granules in a state where the multilayer polymer particles are fused or aggregated at the outermost layer. Shape (hereinafter, may be referred to as aggregated particles). Any of a completely independent form and a form of aggregated particles may be used.

The dispersion state of the multilayer polymer particles in the EVOH is not particularly limited. A state in which the individual multilayer polymer particles are uniformly dispersed in a completely independent form,
A state in which a plurality of multi-layer polymer particles are uniformly dispersed in the form of aggregated particles that are fused or aggregated together, or a state in which completely independent particles and aggregated particles are uniformly dispersed Either state may be used. The multi-layer polymer particles in a dispersed state, including the completely independent form and the form of aggregated particles, preferably have an average particle diameter of 10 μm or less, more preferably 5 μm or less, and more preferably 2 μm or less. It is more preferred that there be. 0.
It is particularly preferable that particles having an average particle diameter in the range of 03 to 1 μm are uniformly dispersed in EVOH. If the particle size of the dispersed particles exceeds 10 μm, it becomes difficult for the multilayer structure polymer particles to be uniformly dispersed in the EVOH matrix, and as a result, the impact strength of the barrier resin (A) layer decreases. The barrier resin (A) may be prepared by dry-blending a powder of EVOH (a1) and multilayer polymer particles (a2). However, from the viewpoint that the barrier resin (A) composed of the EVOH (a1) and the multilayer polymer particles (a2) can obtain a stable morphology and greatly improve the impact resistance of the barrier resin (A) layer. Are preferably mixed by melt-kneading.

The resin composition (B) layer used in the present invention comprises at least one resin (b) selected from the group consisting of a carboxylic acid-modified polyolefin and a boronic acid-modified resin.
1) 1 to 99% by weight and 11 or less solubility parameter other than (b1) (calculated from Fedors equation)
And 1 to 99% by weight of a thermoplastic resin (b2) having

The carboxylic acid-modified polyolefin used as (b1) means a copolymer of an olefin, particularly an α-olefin and an unsaturated carboxylic acid or an anhydride thereof, having a carboxyl group in the molecule. Also included are polyolefins and those in which all or part of the carboxyl groups contained in the polyolefin are present in the form of a metal salt. Examples of the polyolefin serving as the base of the carboxylic acid-modified polyolefin include polyethylene (eg, high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and ultra-low-density polyethylene (VLDPE).
And polyolefins such as polypropylene, copolymerized polypropylene, ethylene-vinyl acetate copolymer, and ethylene- (meth) acrylate copolymer. Among these, from the viewpoint of mechanical strength and durability as the resin composition (B) layer, HDPE, LDPE, L
LDPE and VLDPE are preferred.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate and itaconic acid, and acrylic acid or methacrylic acid is particularly preferred. The content of the unsaturated carboxylic acid is preferably 0.5 to 20 mol%, more preferably 2 to 15 mol%,
More preferably, it is 3 to 12 mol%. Examples of the unsaturated carboxylic anhydride include itaconic anhydride and maleic anhydride, and maleic anhydride is particularly preferred. The content of the unsaturated carboxylic anhydride is preferably 0.0
001 to 5 mol%, more preferably 0.0005 to 3 mol%, further preferably 0.001 to 1 mol%. Among these unsaturated carboxylic acids or anhydrides thereof, from the viewpoint of interlayer adhesion with the barrier resin composition (A) layer,
It is preferred to use maleic anhydride. That is, it is particularly preferable to use a copolymer of an α-olefin and maleic anhydride as the carboxylic acid-modified polyolefin.

Other monomers which may be contained in the copolymer include vinyl esters such as vinyl acetate and vinyl propionate, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, and the like.
Examples include unsaturated carboxylic esters such as n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate, and diethyl maleate, and carbon monoxide.

Examples of the metal ion in the metal salt of the carboxylic acid-modified polyolefin include alkali metals such as lithium, sodium and potassium, alkaline earth metals such as magnesium and calcium, and transition metals such as zinc. The degree of neutralization of the carboxylic acid-modified polyolefin in the metal salt is less than 100%, particularly 90% or less, and more preferably 70% or less.
% Is desirable. Regarding the lower limit of neutralization degree,
Usually, it is preferably at least 5%, particularly preferably at least 10%, further preferably at least 30%.

The carboxylic acid-modified polyolefin used in the present invention has a melt flow rate (MFR) (190 ° C.,
The lower limit of 2160 g load) is 0.01 g / 10 min, preferably 0.05 g / min or more, and more preferably 0.1 g / 10 min or more. The upper limit of MFR is 5
0 g / 10 min or less, more preferably 30 g / 10 min or less,
Optimally, it is desirably 10 g / 10 minutes or less. These carboxylic acid-modified polyolefins can be used alone or in combination of two or more.

The boronic acid-modified resin (b) used in the present invention
1) is a resin having at least one functional group selected from a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water. That is, at least one functional group selected from the group consisting of a boronic acid group, a borinic acid group or a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water is bonded to the main chain by a boron-carbon bond. A resin attached to a chain or terminal.

The carbon of the boron-carbon bond is derived from a base polymer of a resin described later or derived from a boron compound reacted with the base polymer. Preferable examples of the boron-carbon bond include a bond between boron and an alkylene group in a main chain or a terminal or side chain. In the present invention, since a resin having a boronic acid group is suitable, this point will be described below. In the present invention, the boronic acid group is represented by the following formula (I).

[0057]

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The boron-containing group which can be converted into a boronic acid group in the presence of water (hereinafter simply referred to as boron-containing group) is represented by the above formula (I) after hydrolysis in the presence of water. Any boron-containing group that can be converted to a boronic acid group,
Any one may be used, but a typical example is a boron ester group represented by the following general formula (II),
Examples include the boronic anhydride group represented by I) and the boronic acid salt group represented by the following general formula (IV).

[0059]

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[0060]

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[0061]

Embedded image

In the formula, X and Y represent a hydrogen atom, an aliphatic hydrocarbon group (such as a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms) and an alicyclic hydrocarbon group (cyclo Alkyl group, cycloalkenyl group, etc.) and aromatic hydrocarbon group (phenyl group, biphenyl group, etc.)
X and Y may be the same group or different. X and Y may be combined. However, it is excluded when both X and Y are hydrogen atoms. R ¹ , R ² and R ³ represent the same hydrogen atom, aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group as those of X and Y, and R ¹ , R ² and R ³
May be the same group or different. M represents an alkali metal or an alkaline earth metal. X, Y, R ¹ , R ² and R ³ may have other groups such as a carboxyl group and a halogen atom.

Specific examples of the boronic esters represented by the general formulas (II) to (IV) include boronic acid dimethyl ester group, boronic acid diethyl ester group, boronic acid dipropyl ester group, boronic acid diisopropyl ester group,
Dibutyl boronate, dihexyl boronate, dicyclohexyl boronate, ethylene glycol boronate, propylene glycol boronate (1,2-propanediol ester boronate, 1,3-propanediol boronate) Ester group), boronic acid trimethylene glycol ester group, boronic acid neopentyl glycol ester group, boronic acid catechol ester group, boronic acid glycerin ester group,
A boronic ester group such as a boronic acid trimethylolethane ester group; a boronic anhydride group; an alkali metal base of boronic acid, and an alkaline earth metal base of boronic acid. The above-mentioned boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water is a polyolefin,
When hydrolyzed in water or a mixed liquid of water and an organic solvent (toluene, xylene, acetone, etc.) for 10 minutes to 2 hours at a reaction temperature of 25 ° C. to 150 ° C., a boronic acid group or It means a group that can be converted into a borinic acid group.

The content of the functional group is not particularly limited.
It is preferably 0.0001 to 1 meq / g (milli-equivalent / g), and particularly preferably 0.001 to 0.1 meq / g.

The monomers constituting the base polymer of the resin having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group which can be converted to a boronic acid group or a borinic acid group in the presence of water include: Olefinic monomers such as ethylene, propylene, 1-butene, isobutene, 3-methylpentene, 1-hexene, 1-octene and the like; styrene; Styrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 2,4 6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dik Styrenes such as lorostyrene, methoxystyrene and t-butoxystyrene; vinyl-containing aromatic compounds such as vinyl naphthalenes such as 1-vinylnaphthalene and 2-vinylnaphthalene; vinylene-containing aromatic compounds such as indene and acenaphthylene; Vinyl aromatic compounds exemplified, butadiene, isoprene,
Conjugated diene compounds typified by 2,3-dimethylbutadiene, pentadiene, hexadiene and the like can be mentioned.

The base polymer is used as a polymer composed of one, two, or three or more of these monomers. Among these base polymers, especially ethylene-based polymer ｛ultra low density polyethylene, low density polyethylene,
Medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, metal salt of ethylene-acrylic acid copolymer (Na, K, Zn ionomer) ), Ethylene-propylene copolymer｝, and a copolymer of a vinyl aromatic compound and a conjugated diene compound.

Next, typical examples of the resin having at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group which can be converted into a boronic acid group or a borinic acid group in the presence of water, which are used in the present invention. The typical production method will be described. A resin having at least one functional group selected from a boronic acid group, a borinic acid group, and a boron-containing group that can be converted into a boronic acid group or a borinic acid group in the presence of water is a carbon-carbon double bond under a nitrogen atmosphere. By reacting a borane complex and a trialkyl borate with a resin having
After obtaining a resin having a boronic acid dialkyl ester group,
It is obtained by reacting water or alcohols. If a resin having a double bond at a terminal is used as a raw material in this process, a resin having a boronic acid group or a boron-containing group that can be converted to a boronic acid group by the presence of water at the terminal is obtained, and a side chain or a main chain is obtained. When a resin having a double bond is used as a raw material, a resin having a boronic acid group or a boron-containing group which can be converted into a boronic acid group in the presence of water in a side chain can be obtained.

Typical examples of the method for producing a resin having a double bond as a raw material include: (1) a method using a trace amount of a double bond existing at a terminal of an ordinary olefin-based polymer; A process for thermally decomposing the union under oxygen-free conditions to obtain an olefin polymer having a double bond at a terminal; (3)
A method for obtaining a copolymer of an olefin monomer and a diene monomer by copolymerizing an olefin monomer and a diene polymer; (4) a method of producing a copolymer of a vinyl aromatic compound and a conjugated diene monomer. A method for obtaining a copolymer; As for 1), a known method for producing an olefin polymer can be used, and in particular, a method (for example, DE 4030399) using a metallocene polymerization catalyst as a polymerization catalyst without using hydrogen as a chain transfer agent is preferable. Regarding (2), a known method (for example, US Pat. No. 2,835,559,308)
7922) by pyrolyzing the olefin polymer at a temperature of 300 ° C. to 500 ° C. under an oxygen-free condition such as a nitrogen atmosphere or a vacuum condition. Regarding (3), a method for producing an olefin-diene-based polymer using a known Ziegler-based catalyst (for example, JP-A-50-44281, D
E3021273) can be used.

By using the olefin polymer having a double bond obtained by the above-mentioned methods (1) and (2) as a raw material, a boronic acid group, a borinic acid group, and boron in the presence of water can be obtained. A polyolefin having at least one functional group selected from a boron-containing group that can be converted into an acid group or a borinic acid group is obtained. Further, by using the olefin polymer having a double bond obtained by the method (3) and the copolymer comprising the vinyl aromatic compound and the conjugated diene compound obtained by the method (4) as the raw materials, A resin having a functional group bonded to a side chain is obtained.

As the borane complex, a borane-tetrahydrofuran complex, a borane-dimethylsulfide complex, a borane-pyridine complex, a borane-trimethylamine complex, a borane-triethylamine and the like are preferable. Among these, a borane-triethylamine complex and a borane-trimethylamine complex are more preferred. The amount of the borane complex charged is preferably in the range of 1/3 equivalent to 10 equivalents to the double bond of the base polymer. As the trialkyl borate, lower alkyl borate esters such as trimethyl borate, triethyl borate, tripropyl borate and tributyl borate are preferable. The amount of trialkyl borate to be charged is preferably in the range of 1 to 100 equivalents based on the double bond of the olefin polymer. It is not necessary to use a solvent, but if used, hexane,
Saturated hydrocarbon solvents such as hebutane, octane, decane, dodecane, cyclohexane, ethylcyclohexane and decalin are preferred.

The reaction to be introduced is performed at a reaction temperature of 25 ° C. to 300
° C, preferably 100-250 ° C, reaction time 1 minute-10
Time, preferably 5 minutes to 5 hours.

As a condition for reacting water or an alcohol, an organic solvent such as toluene, xylene, acetone or ethyl acetate is usually used as a reaction solvent, and water or an alcohol such as methanol, ethanol, butanol; 2-propanediol, 1.3
-Propanediol, neopentelglycol, glycerin, trimethylolethane, pentaerythritol,
Using a polyhydric alcohol such as dipentaerythritol in a large excess of 1 to 100
It is obtained by performing the reaction at a temperature of 5 ° C to 150 ° C for about 1 minute to 1 day. In addition, the boron-containing group which can be converted into a boronic acid group among the above functional groups refers to a reaction time of 10 minutes to 2 hours in water or a mixed solvent of water and an organic solvent (toluene, xylene, acetone, etc.). , Reaction temperature 25 ° C ~ 15
It means a group that can be converted into a boronic acid group when hydrolyzed at 0 ° C.

When a boronic acid-modified resin is used as (b1), when (b2) is high-density polyethylene, from the viewpoint of compatibility with high-density polyethylene,
Preferably, polyethylene is used as the base polymer.
In particular, a polyethylene having at least one functional group selected from a boronic acid group, a borinic acid group, and a boron-containing group that can be converted to a boronic acid group or a borinic acid group in the presence of water is preferable. On the other hand, when emphasis is placed on the effect of improving the interlayer adhesion between the barrier resin composition (A) and the resin composition (B) layer, a boronic acid group, a borinic acid group, and a boronic acid group in the presence of water are added to the side chains. Alternatively, it is preferable to use a resin having at least one functional group selected from boron-containing groups that can be converted into borinic acid groups. As such a base polymer, a copolymer comprising a vinyl aromatic compound and a conjugated diene compound is preferable. Particularly when the possibility of contact with gasoline is large, at least one functional group selected from a boronic acid group, a borinic acid group and a boron-containing group which can be converted to a boronic acid group or a borinic acid group in the presence of water at the terminal The boronic acid-modified polyethylene having the following is more preferable.

The thermoplastic resin having a solubility parameter of 11 or less used as (b2) includes polyolefin-based resins, styrene-based resins, and polyvinyl chloride-based resins. Since the outermost layer of the fuel container body is usually a polyolefin-based resin, the thermoplastic resin (b
When the solubility parameter of 2) exceeds 11, the heat-fusibility of the molded part for a fuel container of the present invention with the tank body becomes insufficient. As the polyolefin-based resin, a high-density or low-density polyethylene, polypropylene, a homopolymer of α-olefin such as polybutene-1, ethylene,
Copolymers of α-olefins selected from propylene, butene-1, hexene-1 and the like are exemplified. As the styrene resin, polystyrene, acrylonitrile-butadiene-styrene copolymer resin (AB
S), an acrylonitrile-styrene copolymer resin (A
S), a block copolymer with styrene-isobutylene,
Styrene-butadiene copolymer or styrene-
And block copolymers with isoprene. As the thermoplastic resin (b2), the resins exemplified above can be used alone or in combination of two or more.

Among these thermoplastic resins (b2) having a solubility parameter of 11 or less (calculated from the Fedors equation), it is preferable to use a polyolefin resin, and it is more preferable to use a high-density polyethylene. The density of high density polyethylene is 0.93g / cm
It is preferably at least ³ , more preferably 0.93
5 g / cm ³ or more, more preferably 0.94 g / cm ³
cm ³ or more.

The preferred melt flow rate (MFR) of the high-density polyethylene used in the present invention (190 ° C., 21
The lower limit of (under a load of 60 g) is 0.01 g / 10 min, preferably 0.05 g / min or more, more preferably 0.1 g / min or more.
g / 10 minutes or more. The upper limit of the MFR is 50 g /
It is preferably 10 minutes or less, more preferably 30 g
/ 10 min or less, optimally 10 g / 10 min or less.

As described above, the resin composition (B) layer used in the present invention comprises 1 to 99% by weight of at least one resin (b1) selected from the group consisting of a carboxylic acid-modified polyolefin and a boronic acid-modified resin; 1 to 99% by weight of a thermoplastic resin (b2) having a solubility parameter of 11 or less (calculated from the Fedors equation) other than the above (b1)
And a resin composition comprising:

When (b1) is composed of a carboxylic acid-modified polyolefin, the layer (B) is a resin composition comprising 10 to 90% by weight of (b1) and 10 to 90% by weight of (b2). It is preferable from the viewpoint of interlayer adhesion with the resin composition (A) layer. The composition of the layer (B) is (b1)
The content is more preferably 20 to 80% by weight and (b2) 20 to 80% by weight, and particularly preferably (b1) 30 to 70% by weight and (b2) 30 to 70% by weight.

On the other hand, when (b1) comprises a boronic acid-modified resin, the (B) layer may be a resin composition comprising 5 to 95% by weight of (b1) and 5 to 95% by weight of (b2). , (B) from the viewpoint of the balance between the mechanical strength and the interlayer adhesion between the (B) and (A) layers. (B)
The composition of the layer is (b1) 5 to 80% by weight and (b2) 2
The content is more preferably 0 to 95% by weight, and (b1) 5
It is particularly preferred that the content is 60 to 60% by weight and (b2) 40 to 95% by weight.

The resin (b1) and the resin (b2)
Is not particularly limited with respect to the method for obtaining the resin composition (B) by blending the resin with the resin (b1) and the resin (b2). It can be provided, or more preferably, kneaded with a Banbury mixer, a single screw or twin screw extruder, pelletized, and then subjected to melt molding. In order to make the dispersion state uniform and prevent the generation and mixing of gels and bumps, use a high kneading extruder during the kneading and pelletizing operation, seal the hopper port with nitrogen, and extrude at low temperature. desirable.

In the multilayer molded part of the present invention, it is also preferable that the barrier resin composition (A) layer and / or the resin composition (B) layer contain 1 to 50% by weight of an inorganic filler. Preferred examples of the inorganic filler used in the present invention include, but are not particularly limited to, mica, sericite, glass flake, and talc. These inorganic fillers can be used alone or as a mixture of a plurality. The inorganic filler may be added to either the barrier resin composition (A) layer or the resin composition (B) layer, or may be added to both. When an inorganic filler is added to the barrier resin composition (A) layer, it is preferable from the viewpoint of improving gasoline barrier properties. Further, when an inorganic filler is added to the resin composition (B) layer, it is possible to obtain improvement effects such as improvement in mechanical strength and improvement in organic solvent resistance typified by reduction of swelling by gasoline. .

In the present invention, the content of the inorganic filler is 1
The content is preferably from 50 to 50% by weight, and the lower limit of the content is more preferably 5% by weight or more, further preferably 10% by weight or more, and most preferably 15% by weight or more. The upper limit of the content is more preferably 45% by weight or less, and further preferably 40% by weight or less. If the amount is less than 1% by weight, the effect of improving mechanical strength and gasoline barrier properties may be unsatisfactory. On the other hand, if it exceeds 50% by weight, abnormal flow tends to occur during molding, causing sink marks, weld lines, etc., and it may not be possible to obtain a molded article with good appearance.

When at least one of the layer of the barrier resin composition (A) and the layer of the resin composition (B) used in the present invention is a resin composition containing an inorganic filler, each component is mixed by a usual melt-kneading apparatus. The desired resin composition can be easily obtained by melt-kneading. The method of blending each component is not particularly limited, and examples thereof include a method of melt-kneading with a single-screw or twin-screw extruder or the like, and pelletizing and drying. In the melt compounding operation, there is a possibility that the blend becomes non-uniform, and gels and lumps are generated and mixed.Therefore, in the case of blend pelletization, use an extruder with a high degree of kneading as much as possible, and use a nitrogen gas It is desirable to extrude at a low temperature.

The layer structure of the multilayer molded article for a fuel container of the present invention is not particularly limited. When the barrier resin composition (A) layer is A and the resin composition (B) layer is B, (outer) A / B
(Inside), (outside) B / A (inside), (outside) B / A / B
(Inner), (Outer) B / A / B / A / B (Inner) and the like are exemplified as suitable ones. In particular, when the multilayer molded part for a fuel container of the present invention is molded by a two-color molding machine, the A / B configuration is preferable from the viewpoint of ease of molding. On the other hand, in the case of molding by co-injection molding, (outside) A / B
(Inside), (outside) B / A (inside), (outside) B / A / B (inside)
It is preferable to have the following configuration. When emphasis is placed on ease of molding and ease of mold design, (outside) A /
It is particularly preferable to have a two-layer structure of B (inside) or (outside) B / A (inside). Here, (inner) indicates the inner layer side, that is, the layer on the side that directly contacts the fuel. Also,
As long as the effects of the present invention are not impaired, the resin composition (B) layer may have a multilayer structure, and may have a multilayer structure including an adhesive resin layer and a polyolefin resin layer, or a resin composition (B). ) And a resin composition layer (such as a recovery layer) formed by blending a barrier resin composition (A) and a polyolefin-based resin layer.

The thickness of each layer is not particularly limited. Since the gasoline barrier property of the barrier resin composition (A) layer varies depending on the amount of EVOH (a1) contained in the above (A), the gasoline barrier performance required for a multilayer molded part and the barrier resin composition It is preferable to set the thickness of the layer (A) in consideration of the gasoline barrier property of (A). Furthermore, a certain thickness is required from the viewpoint of ease of molding at the time of injection molding. This thickness configuration needs to be set by this formability.

Further, as described above, when the ease of molding and the ease of designing a mold are particularly emphasized, the multilayer molded part of the present invention has two types of (A) layer / (B) layer. It is preferable to have a layer configuration of layers. When having such a layer configuration,
(A) The thickness of the layer is preferably from 10 to 90% of the total layer thickness, preferably from 20 to 80%, and more preferably from 30 to 80%.
More preferably, it is 70%.

As a method for obtaining the multilayer molded part for a fuel container of the present invention, for example, an appropriate molding method in the field of general polyolefin is used, and the multilayer molded part for a fuel container exemplified by a connector, a cap, a valve and the like is used. Since parts generally have complicated shapes, it is particularly preferable to mold them by a multilayer injection molding method. Examples of the multilayer injection molding include two-color molding, insert injection molding, and co-injection molding, and are appropriately selected depending on the shape of a target molded product,
There is no particular limitation. Further, as described above, when the ease of molding and the ease of designing a mold are particularly emphasized, the multilayer molded part of the present invention is a two-layered two-layered (A) layer / (B) layer. Although it is preferable to have a structure, when manufacturing a multilayer molded product having such a layer structure, it is preferable to manufacture using a two-color molding machine.

Here, the two-color molding refers to, for example, using a molding machine having two sets of injection mechanisms and injecting the barrier resin composition (A) or the resin composition (B) melted into a single mold. Thereafter, the resin composition (B) or the barrier resin composition (A) is injected. For the two-color molding, a method in which the mold is inverted has been conventionally used, but a core-back method or the like can be appropriately selected and is not particularly limited. Examples of the mold reversal method include, for example, (1) after injecting the barrier resin composition (A), inverting the mold, and subsequently injecting the resin composition (B) to obtain the barrier resin composition ( A) a method for obtaining a two-layer structure of a layer / a resin composition (B) layer,
(2) First, after injecting the resin composition (B), the mold is turned over, and then the barrier resin composition (A) is injected, and the barrier resin composition (A) layer / resin composition (B) A method for obtaining a two-layer structure of the layers, (3) after injecting the resin composition (B), inverting the mold to inject the barrier resin composition (A), and inverting the mold again to invert the resin composition ( There is a method of injecting B) to obtain a three-layer structure of a resin composition (B) layer / a barrier resin composition (A) layer / a resin composition (B) layer, but the method is not particularly limited.

In the insert injection molding, for example, a molded article which has been molded in advance is mounted on a mold and then subjected to injection molding. For example, after a molded article composed of the barrier resin composition (A) or a molded article composed of the resin composition (B) is obtained by injection molding, the molded article is mounted on an insert injection molding machine, and the resin composition (B) is obtained. And / or a two-layer component composed of a barrier resin composition (A) layer / resin composition (B) layer and a resin composition (B) layer / barrier obtained by injecting the barrier resin composition (A). Examples thereof include a three-layer component of a conductive resin composition (A) layer / a resin composition (B) layer, but are not particularly limited.

Co-injection molding is a process in which, for example, a molding machine having two injection cylinders is used to perform a single clamping operation on a single mold, and the molten barrier resin composition (A) and resin composition (B) The layer is obtained by alternately injecting the layers from the respective injection cylinders into the concentric nozzles at a shifted timing, or simultaneously injecting the layers into the concentric nozzles. For example, (1) the resin composition (B) layer for the inner and outer layers is first injected, and then the barrier resin composition (A) serving as the intermediate layer is injected, and the resin composition (B) layer / barrier property A method of obtaining a molded article having a three-layer structure of the resin composition (A) layer / the resin composition (B) layer, or (2) first injecting the resin composition (B) layer for the inner and outer layers, and then barrier properties The resin composition (A) is injected, and simultaneously or after that, the resin composition (B) layer is injected again, and the resin composition (B) layer / barrier resin composition (A) layer / resin composition ( B) Layer /
Examples include a method of obtaining a molded article having a five-layer structure of a barrier resin composition (A) / resin composition (B) layer, but the method is not particularly limited.

The molded part for a fuel container of the present invention refers to a molded part used by being mounted on a fuel container main body, and specifically includes a fuel container connector, a fuel container cap, a fuel container valve, and the like. But not limited to this. Preferably, it is a fuel container connector and a fuel container valve.

The method of mounting the molded part on the fuel container main body is not particularly limited.
Although mounting by heat fusion is exemplified, mounting by heat fusion is particularly preferable from the viewpoint of reducing the number of assembly steps and suppressing fuel leakage from the mounting portion. A general method is used for heat fusion, and after the fusion surface of the fuel container body and / or the molded part for the fuel container is heated by a heater or the like, a method of performing fusion, the fuel container body and the molded part are separated. Examples include, but are not limited to, a method of performing high-frequency fusion and a method of performing ultrasonic fusion between the fuel container body and the molded component.

Examples of use of the molded component as the molded component connector include a mode in which the molded component is used as a connector for a fuel container mounted on a fuel container body, and a mode in which a flexible fuel transport pipe is mounted. However, the present invention is not limited to these. Examples of the method of attaching this connector to the fuel container body include a screw-in type, a plug-in type, and joining by heat fusion.However, from the viewpoint of reducing the number of assembly steps and suppressing fuel leakage from the joining portion, a method of attaching the connector is described. It is preferable to be mounted by fusion. For this reason, it is particularly preferable that this connector is excellent in the heat fusion property with the fuel container body. It is particularly preferable that the connector has excellent gasoline barrier properties in order to suppress fuel leakage from the fuel container body and the mounting portion of the connector. Further, it is preferable that the connector has excellent stress crack resistance and organic solvent resistance from the viewpoint of long-term continuous use of a molded part for a fuel container, that is, from the viewpoint of product life.

In a preferred embodiment of the fuel container connector, a more flexible fuel transport pipe is joined to the fuel container connector joined to the fuel container body. Therefore, when the vehicle is running, when fuel is supplied from the fuel container to the engine, or when fuel is received from the fuel supply port into the fuel container, continuous connection to the connector due to vibration of the fuel container itself or vibration of the transport pipe is caused. Load occurs. From these viewpoints, the fuel container connector has impact resistance, stress crack resistance,
It is desirable to have excellent organic solvent resistance.

The fuel container cap is used as a lid for a fuel filler. The joining method is not particularly limited,
A screw-in type, a fitting type and the like are exemplified, and a screw-in type is preferable. At present, many fuel container caps are made of metal, but thermoplastic resin caps have attracted attention in recent years from the viewpoint of weight reduction and recycling. Also,
The fuel filler port is connected to the fuel container body via the fuel filler pipe and the fuel container connector.Conventionally, however, there has been a problem of metal oxide mixing into the fuel container due to rust generated from the metal fuel container cap. . From such a viewpoint, the existence of the cap made of the thermoplastic resin is significant. Such a fuel container cap preferably has excellent gasoline barrier properties, organic solvent resistance, and stress crack resistance, and more preferably has excellent mechanical strength such as abrasion resistance because of repeated opening and closing.

A fuel container in which a component made of the thermosetting resin (C) is mounted via a molded component on a fuel container main body on which the molded component is mounted is also suitable as an embodiment of the present invention. . In the fuel container having the above-described structure, the component made of the thermosetting resin (C) has mechanical strength and excellent gasoline barrier properties, and the part made of the thermosetting resin (C) and the fuel container main body are attached to each other. Intervening a molded part made of the resin composition of the present invention is preferable in that high gasoline barrier properties can be imparted. As the thermosetting resin (C), it is particularly preferable to use a polymethylene oxide-based resin from the viewpoint of mechanical strength, gasoline barrier properties, and the like. Although the molded part for a fuel container mounted on the fuel container by such a configuration is not particularly limited, a pressure release valve for a fuel container is preferable.

The method of mounting the component made of the thermosetting resin (C) to the fuel container via the molded component is not particularly limited. First, a molded part is mounted on the fuel container body, and then a fuel container part made of the thermosetting resin (C) is mounted on the molded part by a method such as a screw-in type or a plug-in type. A method of mounting the molded component on a component made of the thermosetting resin (C) and then mounting the molded component on the fuel container body is exemplified, but is not particularly limited.

The method for mounting the molded part on the fuel container body is not particularly limited. A screw-in type, a fitting type mounting, and a mounting by heat fusion are exemplified, but the mounting by heat fusion is particularly preferable from the viewpoint of reducing the number of assembling steps and suppressing fuel leakage from the mounting portion.

The method for mounting the molded component on the component made of the thermosetting resin (C) is not particularly limited. Screw-in type,
A filling-type method is preferred. Further, a method of coating the joint surface between the component made of the thermosetting resin (C) and the fuel container with the resin composition used in the present invention is also suitable. Since the thermosetting resin (C) and the resin composition used in the present invention generally have low adhesiveness, the surface of the component made of the thermosetting resin (C) must be within a range that does not impair the function of the molded component. It is particularly preferable to coat as much as possible with the resin composition used in the present invention. By employing such a configuration, it is possible to suppress separation at the interface between the molded component body made of the thermosetting resin (C) and the resin composition of the present invention.

The method of coating the molded component body with the resin composition used in the present invention is not particularly limited, but the component body made of the thermosetting resin (C) previously prepared by the injection molding method or the like is used in a mold. In which the resin composition of the present invention is injected and coated with an injection molding machine (insert injection method), or the thermosetting resin (C) and the resin composition used in the present invention are co-injected. Although a molding method and the like are mentioned as preferable examples, an insert injection method is particularly preferable.

[0101]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Materials Used) Resins and resin compositions used for producing molded parts for fuel containers of Examples and Comparative Examples of the present invention are shown in Table 1 below.

[0103]

[Table 1]

Synthesis Example 1 Synthesis of Multilayered Polymer Particles (a-2) Under a nitrogen atmosphere, 600 parts by weight of distilled water, lauryl sarcosine as an emulsifier were placed in a polymerization vessel equipped with a stirring blade, a cooling pipe and a dropping funnel. 0.136 parts by weight of sodium and 1.7 parts by weight of sodium stearate were added, and the mixture was heated to 70 ° C. and uniformly dissolved. Then, at the same temperature,
100 parts by weight of butyl acrylate, 60 ethyl acrylate
After adding 2.0 parts by weight of allyl methacrylate as a polyfunctional polymerizable monomer and stirring for 30 minutes, 0.15 parts by weight of potassium peroxodisulfate was added to initiate polymerization. After 4 hours, gas chromatography confirmed that all the monomers had been consumed.

Next, 0.3 parts by weight of potassium peroxodisulfate was added to the obtained copolymer latex, and then 60 parts by weight of methyl methacrylate, 20 parts by weight of methacrylic acid and n-octyl mercaptan 0 as a chain transfer agent were added. .
One part by weight of the mixture was dropped from the dropping funnel over 2 hours. After the completion of the dropwise addition, the reaction was continued at 70 ° C. for another 30 minutes, and the polymerization was terminated after confirming that each monomer was consumed. The average particle diameter of the obtained latex was 0.20 μm. This was cooled to −20 ° C. for 24 hours to aggregate, and then the aggregate was taken out and washed three times with hot water at 80 ° C.
Furthermore, it was dried under reduced pressure at 50 ° C. for 2 days to have an inner layer of an acrylic rubber (Tg = −44 ° C.) containing butyl acrylate as a main component, and a hard outermost layer (Tg = Mg) of methyl methacrylate and methacrylic acid. 128 ° C.) to obtain polymer particles having a two-layer structure. The particle diameter of the multilayer polymer particles in the latex thus obtained was measured by a dynamic light scattering method using a laser particle size analysis system PAR-III (Otsuka Electronics Co., Ltd.). The average particle size of the structural polymer particles was 0.20 μm.

Example 1 Ethylene content 32 mol%, saponification degree 99.5%, M
FR1.6g / 10min (at 190 ℃ -2160g load)
90 parts by weight of the EVOH (a-1) and 10 parts by weight of the multilayer polymer particles (a-2) prepared according to Synthesis Example 1 were placed in a twin-screw vented extruder, and the mixture was exposed to nitrogen in the presence of nitrogen. The mixture was extruded and pelletized at ℃ to obtain a barrier resin (a-3).

On the other hand, MFR 0.3 g / 10 minutes (at 190 ° C.
-2160 g load), 50% by weight of polyethylene (b-1) having a density of 0.952 g / cm ³ and maleic anhydride-modified polyethylene (b-2) ("Admer G" manufactured by Mitsui Chemicals, Inc.
T6A ") was obtained in the following manner. That is, 50 parts by weight of a polyethylene (b-1) having a density of 0.952 g / cm ³ and 50 parts by weight of a maleic anhydride-modified polyethylene (b-2) were put into a twin-screw vented extruder, and were placed in the presence of nitrogen. The pellet was extruded at 220 ° C. to obtain a pellet of the resin composition (b-4).

The resin composition pellet (a-3) was used as the barrier resin composition (A), and the resin composition pellet (b-4) was used as the resin composition (B).
A two-layer, two-layer multilayer molded product having a layer configuration of / (B) was obtained as follows. That is, the pellets (a-3) and (b-4) prepared above were charged into a two-color molding machine, and the inner diameter was 34 mm, the outer diameter was 40 mm, and the height was 75.
A multilayer molded article having a thickness of 2 mm and a shape as shown in FIG. FIG. 2 shows a cross-sectional view of the multilayer molded part.
The layer composition was (outer) resin composition (B) layer / barrier resin composition (A) layer (inner), and the thickness ratio at each part was (outer) 55/45% (inner). . This multilayer molded article has a shape similar to a connector for a fuel container (hereinafter, referred to as a connector-like molded article), and as shown in FIG. 3, the connector-like molded article is attached to an opening provided in the body of the container body. It is used. In a preferred embodiment, the connector-like molding 41 is attached to the container body 42, and a pipe 43 is attached to the mouth of the connector-like molding 41 (FIG. 4).

On the other hand, high density polyethylene (HDPE:
A three-layer five-layer direct blow molding machine using EVOH (a-1) as an intermediate layer and an adhesive resin (maleic anhydride-modified LDPE, Admer GT5A manufactured by Mitsui Chemicals) as inner and outer layers using HZ8200B manufactured by Mitsui Chemicals as inner and outer layers. Thus, an EVOH-based multilayer tank having a capacity of 35 liters and a surface area of 0.85 m ² was produced. The layer structure of this tank is (outside) HDPE / adhesive resin / EVOH (a-1) / adhesive resin / HDPE
(Inner) = 2500/100/150/100/2500
μm.

After opening two openings of 50 mm in diameter in the multilayer tank for mounting a connector, both the outer surface of the tank near the openings and the two-layer, two-layer connector-like molded articles prepared above were removed by 250 mm. After melting with an iron plate at 40 ° C. for 40 seconds, it was pressed and thermally fused to obtain a multilayer tank with two connector-like molded articles. The gasoline barrier property was evaluated by the following method using a multilayer tank to which the multilayer molded article was fused.

(1) Gasoline barrier property 30 liters of model gasoline (toluene: isooctane = 50) was added to the obtained multilayer tank having two openings.
/ 50% by volume). Next, an aluminum plate having a diameter of 60 mm and a thickness of 0.5 mm is firmly bonded to one side of the connector-like molded product with an epoxy-based adhesive, and then placed in an explosion-proof constant temperature / humidity bath (40 ° C.-65% RH). After 60 days, the weight loss (n = 5) was measured (W). As a control, a multilayer sheet (HDPE / adhesive resin / EVOH (a-1) / adhesive resin / HDPE = 2100/100/600/10) obtained using the same resin as the resin used for the multilayer tank.
0/1100 μm was thermally fused to two openings in the same manner as the connector (HDPE having a thickness of 1100 μm).
The layer side was heat-sealed to the tank body, and the weight loss of the model gasoline was measured in the same manner (w). The gasoline reduction from the connector was calculated by the following equation (1). Gasoline decrease from connector = WW (1)

The impact resistance of the multilayer molded part was evaluated according to the following method.

(2) Impact resistance The multilayer molded article produced by the above method was used at 20 ° C. and 65% RH.
After humidity control for 20 days under the conditions of
It was dropped on a concrete floor from a height of 10 m in a room conditioned by RH. The appearance of the multilayer molded article after dropping was visually observed and evaluated.

The interlayer adhesion strength between the barrier resin composition (A) and the resin composition (B) layer was evaluated according to the following method.

(3) Interlaminar Adhesive Strength Using the barrier resin composition (A) and the resin composition (B), a butting type test piece was prepared by a two-color molding machine. Each of the small piece composed of the barrier resin composition (A) and the small piece composed of the resin composition (B) has a length of 12
It is 0 mm, width 50 mm, and thickness 2 mm, and each small piece overlaps 80 mm (FIG. 5). Using such a test piece, an autograph (AG-500A made by Shimadzu)
Was used to determine the 180 ° peel strength.

(4) Heat-fusibility with a fuel tank The connector peripheral portion of a gasoline tank equipped with a connector-like multilayer molded product prepared by the above method is cut out at a diameter of 20 cm around the connector, and the connector-like multilayer is cut out. A multilayer sheet to which the molded article was fused was obtained. Using the multilayer sheet to which the molded article was fused, the strength at which the fused portion was peeled off was determined using an autograph (AG-500A manufactured by Shimadzu). That is, as shown in FIG. 6, the sheet portion of the multilayer sheet to which the molded article has been fused is pressed by the jig (1),
Using a jig (2), the molded article was pulled in the vertical direction with respect to the multilayer sheet, and the peeling strength between the multilayer sheet and the molded article was measured.

In this embodiment, the amount of gasoline permeated from the connector is 0.01 g / 2 pieces.60.
days, indicating good gasoline barrier properties. Moreover, the evaluation result of the impact resistance of the multilayer molded part was A judgment. Further, when a test of the interlayer adhesion strength was performed, good interlayer adhesion was exhibited, in which the layer (B) was broken before the layers (A) and (B) were separated. In addition, even in the test of the heat fusion strength with the fuel tank, the connector-like multilayer molded product is torn while the fusion portion remains fused.
Good fusibility was exhibited.

Example 2 In the same manner as in Example 1, the resin composition pellet (a-3) was used as the barrier resin composition (A), and the resin composition pellet (b-) was used as the resin composition (B). Using 4), each resin composition pellet was charged into a two-color molding machine, and a two-layer, two-layer molded article was produced in the same manner as in Example 1. The layer constitution was (outer) barrier resin composition (A) / resin composition (B) layer (inner), and the thickness ratio at each part was (outer) 45/55% (inner). Using the obtained multilayer molded product, gasoline barrier properties and impact resistance were evaluated in the same manner as in Example 1. Table 2 shows the results.

Synthesis Example 2 Boronate Ethylene Glycol Ester Group
Synthesis of ultra low density polyethylene: (b-3) Separable frus with cooler, stirrer and dropping funnel
Ultra low density polyethylene @ MFR 7g / 10min (21
0 ° C-load 2160 g) Density 0.89 g / cm ^Three, Terminal
Double bond amount 0.048 meq / g @ 1000 g, decal
2,500 g, and degassed by reducing the pressure at room temperature
, Followed by nitrogen substitution. To this, trimethyl borate
And 5.8 g of borane-triethylamine complex.
And reacted at 200 ° C for 4 hours.
Further, 100 ml of methanol was slowly added dropwise. Methano
After the addition of methanol, boric acid and methanol
Distills low boiling impurities such as trimethyl and triethylamine
I left. Further, 31 g of ethylene glycol was added, and 1
After stirring for 0 minutes, reprecipitate in acetone and dry.
And the amount of boronic acid ethylene glycol ester group is 0.02
7 meq / g, MFR 5 g / 10 min (210 ° C.-load 2
160 g) of boronic acid-modified ultra low density polyethylene
Was.

Example 3 Polyethylene having a MFR of 0.3 g / 10 min (at 190 ° C. under a load of 2160 g) and a density of 0.952 g / cm ³ (b-
1) 50 parts by weight and 50 parts by weight of the boronic acid-modified resin (b-3) prepared according to Synthesis Example 2 were put into a twin-screw vented extruder, and extruded at 220 ° C. in the presence of nitrogen to form pellets. Thus, pellets of the resin composition (b-5) were obtained.

A multilayer molded part was produced in the same manner as in Example 1 except that the resin composition (b-5) prepared above was used as the resin composition (B) layer, and gasoline barrier properties and impact resistance were obtained. The sex was evaluated. Table 2 shows the evaluation results. Further, as the barrier resin composition (A), the resin composition (a-
3) Using (b-5) as the resin composition (B), the adhesive strength was tested according to the above method.
Good interlayer adhesion was exhibited, in which the layer (B) was broken before the layers (A) and (B) were separated.

Example 4 A multilayer molded part was produced in the same manner as in Example 2 except that the resin composition (B-5) prepared in Example 3 was used as the resin composition (B) layer. The gasoline barrier properties, impact resistance and thermal fusion properties were evaluated. Table 2 shows the evaluation results.

Comparative Example 1 In Example 1, E was used as the barrier resin composition (A).
A multilayer molded part was produced in the same manner as in Example 1 except that only VOH (a-1) was used, and gasoline barrier properties, impact resistance, and heat fusion properties were evaluated. Table 2 shows the evaluation results. Further, a test piece of two-color molding was prepared in the same manner as in Example 1, and the interlayer adhesion strength was evaluated.
(A-1) ((A) layer) and composition (b-4)
((B) layer) shows good adhesiveness, and (A) layer and (B)
The layer (B) broke before the layer was peeled off.

Comparative Example 2 In Example 1, (b-) was used as the thermoplastic resin (B).
A multilayer molded part was prepared in the same manner as in Example 1 except that only 1) was used, and gasoline barrier properties, impact resistance, and heat fusion properties were evaluated. Table 2 shows the evaluation results. In addition, two-color molded test pieces were prepared in the same manner as in Example 1, except that the barrier resin composition (a-3) ((A) layer) and polyethylene (b-1) ((B) layer) Interlayer adhesion was poor, and peeling occurred between layers (A) and (B) during the work of attaching the autograph to the jig.

Comparative Example 3 Using an injection molding machine, an EVOH (a-) having the same shape as the connector-like molded product (FIG. 1) produced in Example 1 was used.
A single-layer molded product comprising 1) was produced. Using the obtained single-layer molded product, gasoline barrier properties and impact resistance were evaluated in accordance with the above methods. Table 2 shows the results.
In addition, the evaluation of the heat fusibility was attempted in the same manner as in Example 1. However, the heat fusibility of the molded article was poor, and the molded article and the multilayer sheet (molded) were not attached during the work of attaching the autograph to the jig. From the tank body with the product attached).

Comparative Example 4 Using an injection molding machine, a single-layer molded article made of polyethylene (b-1) having the same shape as the connector-like molded article produced in Example 1 (FIG. 1) was produced. Using the obtained single-layer molded product, gasoline barrier properties, impact resistance, and heat fusion properties were evaluated in accordance with the above method. Table 2 shows the results.

[0127]

[Table 2]

The multilayer molded parts of Examples 1 to 4 having the constitution of the present invention were excellent in gasoline barrier properties, impact resistance and heat sealability. Also, the interlayer adhesion between the barrier resin composition (A) layer and the resin composition (B) layer was excellent.

On the other hand, in Comparative Example 1 in which the layer (A) was composed of only EVOH, the impact resistance of the layer (A) was insufficient. Further, in Comparative Example 2 in which the layer (B) was made of only polyethylene, the interlayer adhesion between the layer (A) and the layer (B) was insufficient, and the impact resistance of the multilayer molded part was unsatisfactory. .

In Comparative Example 3 in which the molded product was a single-layer injection molded product composed of only EVOH, sufficient impact resistance and heat-fusibility were not obtained. Furthermore, in Comparative Example 4 in which the molded article was a single-layer injection molded article composed of only polyethylene, sufficient gasoline barrier properties could not be obtained.

[0131]

According to the present invention, it is possible to provide a multilayer molded part for a fuel container excellent in gasoline barrier properties, impact resistance, and heat fusion property, and a fuel container in which the molded part is mounted on a fuel container body. Such a fuel container is particularly suitable for use as an automobile gasoline tank.

[Brief description of the drawings]

FIG. 1 is a view showing a multilayer molded product (connector-like molded product) molded by a two-color molding machine.

FIG. 2 is a cross-sectional view of a multilayer molded product (connector-like molded product) molded by a two-color molding machine.

FIG. 3 is a view showing a usage form of a connector-like molded product.

FIG. 4 is a diagram showing a usage form of a connector-like molded product.

FIG. 5 is a view showing a structure of a test piece for measuring interlayer adhesion strength.

FIG. 6 is a schematic diagram showing a test method for evaluating heat fusion properties.

[Explanation of symbols]

31: Multi-layer molded part (inner layer) mounted on opening of fuel container body 32: Multi-layer molded part (outer layer) mounted on opening of fuel container body 33: Fuel container body (outer layer) 34: Fuel container Main body (intermediate layer) 35: Fuel container main body (inner layer) 41: Connector-like molded article 42: Container main body 43: Pipe 51: Part of test piece composed of barrier resin composition (A) 52: Resin composition ( Part of the test piece consisting of B) 61: Multi-layer connector-like molded product 62: Multi-layer sheet (cut around the opening of the fuel container body on which the molded product is mounted) 63: Jig (1) 64: Jig (2)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B60K 15/03 B65D 25/20 Z B65D 25/20 B29K 9:00 // B29K 9:00 23:00 23 : 00 55:00 55:00 B60K 15/02 ZF term (reference) 3D038 CC19 CC20 3E062 AA06 AB03 AC02 BA20 BB10 4F100 AA00A AA00B AK01A AK01B AK01C AK03B AK05 AK05B AK06 AK25 AK25 BA03 AK01 BA04 BA05 BA10A BA10B BA10C BA15 CA23A CA23B DA01 DE01A EH36 GB16 GB32 JB08B JB13C JB16B JD01 JD01A JD05 JK10 JL12 YY00A YY00B 4F206 AA03E AA03J AA05 JA03 AB07 JA07 AB12 JA03 AB16

Claims (11)

[Claims] 1. An ethylene-vinyl alcohol copolymer (a1) having an ethylene content of 5 to 60 mol% and a saponification degree of 85% or more, 60 to 95% by weight, and a multilayer structure polymer particle (a2) 5 to 40% by weight. A resin composition (A) layer comprising at least one resin (b1) selected from the group consisting of a carboxylic acid-modified polyolefin and a boronic acid-modified resin in an amount of 1 to 99% by weight and 11 other than the above (b1). 1 to 99% by weight of a thermoplastic resin (b2) having the following solubility parameter (calculated from the Fedors equation)
A multilayer molded part for a fuel container, comprising a resin composition (B) layer comprising: 2. The multilayer molded part according to claim 1, wherein the thermoplastic resin (b2) is a high-density polyethylene. 3. The barrier resin composition (A) layer and / or the resin composition (B) layer comprises 1 to 50% by weight of an inorganic filler.
The multilayer molded part for a fuel container according to claim 1 or 2, comprising: 4. The multilayer molded part for a fuel container according to claim 1, wherein the molded part is molded by a multilayer injection molding machine. 5. The multilayer molded part for a fuel container according to claim 4, wherein the molded part is molded by a two-color molding machine, an insert injection molding machine, or a co-injection molding machine. 6. The multilayer molded part for a fuel container according to claim 1, wherein the multilayer molded part for a fuel container is a fuel container connector, a fuel container cap or a fuel container valve. 7. A fuel container wherein the multilayer molded part for a fuel container according to claim 1 is mounted on a fuel container main body via a resin composition (B) layer. 8. A fuel container, wherein the molded part for a fuel container according to claim 1 is attached to a fuel container body by heat fusion. 9. A fuel in which a component made of a thermosetting resin (C) is mounted on a fuel container on which the molded component according to any one of claims 1 to 6 is mounted via the molded component. container. 10. The fuel container according to claim 9, wherein the thermosetting resin (C) is polymethylene oxide. 11. An automotive fuel tank comprising the fuel container according to claim 7.