JPH1095913A - Resin composition and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition excellent in barrier resistance to gasoline and impact resistance, comprising a polyketone as carbon monoxide- ethylene-based copolymer and an ethylene-vinyl alcohol copolymer in specified proportions. SOLUTION: This resin composition comprises (A) 1-65wt.% of a polyketone as carbon monoxide-ethylene-based copolymer and (B) 99-35wt.% of an ethylene- vinyl alcohol copolymer. The component A is pref. an alternate copolymer with raised carbonyl group content in terms of impact resistance and barrier resistance to gasoline. The melt index of the component A at 230 deg.C under a load of 2,160g is pref. 0.1-10g/10min. For the component B, the ethylene content is pref. 22-70mol%,the saponification degree of the vinyl ester component is >=85% and the melt index is 0.5-20g/10min. Furthermore, incorporation of 0.002-0.2mol% of a vinylsilane compound as a comonomer ingredient in the component B improves the melt viscosity consistency with the base resin in conducting a coextrusion, therefore being favorable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an excellent barrier property and impact resistance to gasoline blended with an oxygen-containing component such as gasoline containing automobile fuel, especially gasoline containing methanol or gasoline containing methyl tert-butyl ether (hereinafter abbreviated as MTBE). The present invention relates to a resin composition and a container or pipe using the same, particularly a fuel container or fuel pipe.

[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 of having relatively high permeability. On the other hand, conventionally, there are a method of improving a barrier property by a sulfone treatment or a chlorofluorocarbon treatment in a polyethylene tank, and a method of mixing a substance having a barrier property with polyethylene, for example, nylon. On the other hand, there has been proposed a three-layer, five-layer structure in which a multilayer structure is used, a nylon is used for a barrier layer, and a high-density polyethylene layer is provided on both sides of the barrier layer with an adhesive layer interposed therebetween.

[0003]

However, from the viewpoint of strengthening regulations on environmental pollution in recent years, preventing air pollution and saving gasoline consumption, oxygen-containing components such as methanol and MTBE have been used to improve the octane number of gasoline. (Hereinafter sometimes abbreviated as gas hole) is used mainly in the United States. However,
The above-mentioned conventional tank has a drawback that the gasoline permeation amount from the entire tank increases, and improvement of these drawbacks is desired.

[0004] As means for improving this, a method of forming the above-mentioned multilayer structure of polyethylene and nylon, a method of mixing nylon with polyethylene and simultaneously extruding the same, and dispersing nylon in a discontinuous thin layer in the polyethylene layer,
Further, there is a method in which a multilayer structure is used and nylon is used for a barrier layer. However, these methods have a problem in barrier properties against gasoline blended with an oxygen-containing component. Also,
Even a method of treating a polyethylene monolayer with a sulfone or a fluorine is insufficient in barrier properties against gasoline blended with an oxygen-containing component. An object of the present invention is to provide a resin composition having excellent gasoline barrier properties and impact resistance, and a multilayer structure using the same.

[0005]

An object of the present invention is to provide a polyketone (a) comprising a carbon monoxide-ethylene copolymer.
To provide a resin composition comprising 5% by weight and 99 to 35% by weight of an ethylene-vinyl alcohol copolymer (b), a container molded from the composition, and a fuel container or a fuel pipe using the composition. Is achieved by

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION By providing a fuel container and a fuel pipe having a single-layer or multi-layer structure having the above-mentioned resin composition layer, characteristics excellent in barrier properties against gasoline and gas holes and excellent in impact resistance are provided. This not only complies with environmental issues but also greatly enhances the safety during actual use. Here, the barrier property means a barrier property of fuel such as gasoline or gasoline blended with methanol, MTBE or the like.

In the present invention, the polyketone (a) is
-Carbon oxide-ethylene based copolymer, carbon monoxide-
Ethylene copolymers include those obtained by copolymerizing carbon monoxide and ethylene, or those obtained by copolymerizing carbon monoxide and ethylene as main components with unsaturated compounds other than ethylene. A representative example is given. Here, examples of the unsaturated compound other than ethylene include an olefin having 3 to 12 carbon atoms, a diene having 4 to 12 carbon atoms, a vinyl ester, and an aliphatic unsaturated carboxylic acid ester. Examples of the copolymer include a random copolymer and an alternating copolymer, and an alternating copolymer having a high carbonyl group content is preferable in terms of impact resistance and barrier properties.

The olefin having 3 to 12 carbon atoms includes propylene, butene-1, isobutene, pentene-
Examples thereof include 1,4-methylpentene-1, hexene-1, octene-1, dodecene-1, and styrene, and propylene, an olefin having 4 to 8 carbon atoms, or a combination thereof is preferable. Examples of the diene having 4 to 12 carbon atoms include butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene, and 1,9-decadiene. Examples of vinyl esters include vinyl acetate, vinyl propionate, and vinyl pivalate. In addition, aliphatic unsaturated carboxylic acids, salts and esters thereof, acrylic acid, methacrylic acid,
Maleic anhydride, maleic acid, itaconic acid, acrylic ester, methacrylic ester, maleic monoester, maleic diester, fumaric monoester,
Fumaric acid diester, itaconic acid monoester, itaconic acid diester (these esters include methyl esters, alkyl esters such as ethyl esters, etc.),
Acrylates, maleates, and itaconates (these salts include monovalent or divalent metal salts).

As a method for producing the polyketone, known methods, for example, US Pat. No. 2,495,286, JP-A-53-128690, and JP-A-59-197427
JP-A-61-91226, JP-A-62-2324
No. 34, JP-A-62-53332, JP-A-63-30
No. 25, JP-A-63-105031, JP-A-63-1
No. 54737, JP-A-1-149829, JP-A-1-149829
No. 2013333, JP-A-2-67319 and the like, but are not particularly limited thereto.

The melt index (MI) of the polyketone used in the present invention is preferably 0.01 to 50 g / 10 min (at 230 ° C. under a load of 2160 g), and most preferably 0.1 to 1 g.
0 g / 10 minutes. When the MI is in the above range, the fluidity of the resin is excellent, and the moldability is also excellent.

In the present invention, EVOH (b) is a saponified ethylene-vinyl ester copolymer, and preferably has an ethylene content of 20 to 80 mol%, more preferably 2 to 80 mol%.
The saponification degree of the vinyl ester component is preferably 80% or more, and more preferably 85% or more. If the ethylene content is less than 20 mol%, melt moldability is poor, and barrier properties and thermal stability are poor. As a vinyl ester, vinyl acetate is mentioned as a typical example, but other fatty acid vinyl esters (vinyl propionate, vinyl pivalate, etc.) can also be used. Also,
A vinylsilane compound 0.0 as a copolymer component in EVOH
When 002-0.2 mol% is contained, the consistency of the melt viscosity with the base resin at the time of co-extrusion is improved, and not only can a homogeneous co-extruded multilayer film be produced, but also EVO can be produced.
The dispersibility when H is used for blending 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. Furthermore, as long as the object of the present invention is not inhibited,
Other comonomers [e.g., propylene, butylene, unsaturated carboxylic acids or esters thereof (meth) acrylic acid,
(Meth) acrylate methyl, ethyl), etc.
Vinyl pyrrolidone (such as N-vinyl pyrrolidone) can also be blended. Also, the EVOH used in the present invention
Suitable melt index (MI) (230 ° C., 21
(Measured under a load of 60 g) is 0.1 to 50 g / 10
Minute. , 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 saponification degrees in a blended state.

The polyketone (a) and the EVOH
As for the mixing of (b), the polyketone (a) 1-65% by weight and the ethylene vinyl alcohol copolymer (b) 99-
It can be performed at 35% by weight. The content of EVOH (b) is 95 to 35% by weight, preferably 85 to 40% by weight, and more preferably 75 to 45% by weight. When the content of (a) is 1% by weight or less, the resulting containers and pipes have insufficient impact resistance, and when the content of (b) is 35% by weight or less, the barrier properties are extremely high. It becomes difficult to maintain. In order to properly impart impact resistance and barrier properties, 65 to 30% by weight of polyketone (a) and EVO
H (b) is preferably 35 to 70% by weight, more preferably 60 to 40% by weight of polyketone (a) and E
VOH (b) is 40 to 60% by weight.

Further, the resin composition of the present invention may contain various additives as required. Examples of such additives include antioxidants, plasticizers, heat stabilizers,
UV absorbers, antistatic agents, lubricants, coloring agents, fillers,
Alternatively, other polymer compounds can be mentioned, and these can be blended as long as the effects of the present invention are not inhibited. 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'-diphenylacrylate, 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 also be blended to such an extent that the effects of the present invention are not impaired.

In the present invention, the recovered scrap can be mixed with the virgin polyketone as required. Examples of the mixing method include a dry blending method and a melt kneading method. However, if the ratio of scraps collected to virgin pellets exceeds 50%,
Problems may occur in terms of thermal stability and impact resistance. Here, as the scrap recovered material, a hollow container, a tubular container,
In addition, there is a molding loss portion generated when a molded article such as a tubular body is produced, and a crushed scrap recovered article used by general consumers.

The thickness of the container intended by the present invention, in particular, the thickness of the fuel container is not particularly limited.
From the viewpoint of impact resistance, the total layer thickness is 1500 to 10000 μm, preferably 2000 to 7000 μm. These thicknesses refer to the thickness of the body of a container such as a fuel container.

The method for obtaining the container or pipe of the present invention is not particularly limited. For example, molding methods used in the field of general polyolefins, such as blow molding, stretch blow molding, and Examples thereof include blow molding and injection molding, and a blow molding method is particularly preferable.

By using the thus obtained container and pipe as a fuel container and a fuel pipe, excellent barrier properties and impact resistance to gasoline and other fuels can be obtained, as shown in Examples described later. Granted.

In the present invention, the fuel container 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. Further, it means a container for storing fuel used for these operations.
The fuel pipe is a pipe attached to the fuel container mounted above, or a portable container for replenishing the fuel container with fuel, and a container for storing the fuel used for the operation. Etc. or a pipe independent of itself. Typical examples of the fuel include gasoline blended with gasoline, methanol and / or MTBE, and other heavy oils and petroleum are also exemplified. Among them, the fuel container or pipe of the present invention is particularly effective for gasoline blended with methanol and / or MTBE.

[0021]

EXAMPLES Examples and comparative examples are shown below. Example 1 In a 100 liter autoclave, methanol 20 was added.
Liters, 4 mmol of palladium acetate, 6 mmol of 1,3-di (diphenylphosphane) propane and 80 mmol of p-toluenesulfonic acid, which were flushed with carbon monoxide and treated with 35 bar of carbon monoxide and 18 bar.
The autoclave was filled and reacted with ethylene at a pressure of bar to obtain a polyketone (PK) composed of an ethylene-carbon monoxide alternating copolymer. To the obtained polyketone, 1000 ppm of calcium hydroxyapatite was added and pelletized by an extruder, and the weight average molecular weight was 180,000, the number average molecular weight was 63,000, and MI = 6.1 g / 10 min (23
A pellet at 0 ° C. under a load of 2160 g) was obtained. EVOH ペ レ ッ ト ethylene content 27 mol%, saponification degree 99.
6%, melt index 6.0 g / 10 min (230
C., 2160 g load) was blended at a ratio of 60 to 40 (weight ratio) and melt-mixed with a twin-screw extruder (TEX30: manufactured by Nippon Steel Works) to obtain pellets. Using these pellets, blow molding machine (TB-ST-6P, manufactured by Suzuki Seisakusho)
To obtain a 500 cc (average body thickness: 2500 μ) container.

In the container obtained, a mixture of model gasoline / toluene (42.5% by weight): isooctane (42.5% by weight): methanol (15% by weight), capacity: 250
Then, the mixture was left in an atmosphere of 40 ° C. and 65% RH, and the weight loss after 4 days was determined. (N = 10)

Next, the same container as above was filled with water and dropped on concrete, and the drop height at which the bottle was destroyed (water inside the container leaked) was determined. Breaking height (20 ℃-
65% RH) was determined according to JIS using the test results of n = 30.
The 50% breaking height was determined using the calculation method shown in the test method (the section “8. Calculation” of K7211).

Example 2 A container was obtained in the same manner as in Example 1 except that the mixing ratio of polyketone and EVOH was changed to 40:60 (weight ratio). Table 1 shows the results.

COMPARATIVE EXAMPLE 1 6-nylon {melt index 2.3 g / 10 min (230 ° C., 2160 g load)} was used as an intermediate layer, and high density polyethylene (HDPE) MI = 0.4 g / 10 min (230 ° C., 2160g load)｝, density 0.96g / c
m ³ , “HZ8200B” manufactured by Mitsui Petrochemical Co., Ltd. as an outer layer, and further, a maleic anhydride-modified polyethylene {MI = 2.0 g / 10 min (230 ° C., 216
0 g load), 3 types and 5 layers (HDPE / adhesive layer / 6 nylon / adhesive layer / HDPE = 1163/50/7) by co-extrusion blow molding using "Admer GT4" manufactured by Mitsui Petrochemical Co., Ltd.
(5/50/1163 μ) was obtained.
Hereinafter, a gasoline barrier property and an impact resistance test were performed in the same manner as in Example 1.

Comparative Example 2 A mixture of the polyketone and EVOH shown in Example 1 was mixed with high-density polyethylene (HDPE) @ MI = 0.4 g / 10 min (230 ° C., 2160 g load), density 0.96 g / cm
^{3. A} gasoline barrier property and impact resistance test were carried out in the same manner as in Example 1 except that "HZ8200B" manufactured by Mitsui Petrochemical Co., Ltd. was changed.

Comparative Example 3 A mixture of the polyketone and EVOH shown in Example 1 was used for EV
A gasoline barrier property and impact resistance test were performed in the same manner as in Example 1 except that only OH was changed.

[0028]

[Table 1]

[0029]

According to the present invention, containers and pipes, especially fuel containers and fuel pipes, having excellent impact resistance and excellent barrier properties against fuels such as gasoline blended with oxygen-containing components such as methanol can be obtained.

Claims (3)

[Claims] 1. A resin composition comprising 1 to 65% by weight of a polyketone (a) composed of a carbon monoxide-ethylene copolymer and 99 to 35% by weight of an ethylene-vinyl alcohol copolymer (b). 2. A container or pipe formed from the resin composition according to claim 1. 3. A fuel container or fuel pipe comprising the resin composition according to claim 1.