JP2002121334A - Resin structure, vessel for carrying and/or storing of chemical or gas, and its attachment parts - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin structure having gas and/or liquid permeation resistance even in a use under a high humidity, and having excellent characteristics in a water-absorbing state, without such as a dimensional change nor the deterioration in mechanical properties such as toughness and so on. SOLUTION: The resinous structure comprises a resin composition consisting of 5-80% by volume of a polyketone resin and 95-20% by volume of a polyolefin resin and has a phase structure, as a resin phase-separating structure observed with an electron microscope, in which structure the polyolefin resin is of a continuous phase and the polyketone resin is of a beltlike dispersed structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure having excellent resistance to gas and / or liquid permeation.
In particular, the present invention relates to a resin structure having specific resistance to permeation, high impact resistance, and thermal stability, which is suitable for application to gas and / or liquid barrier components.

[0002]

2. Description of the Related Art Polyketone resins have been used as molded articles around various automotive fuels because of their excellent fuel stability and gas barrier properties.

However, the impact strength of the polyketone resin is superior to that of nylon 6 and nylon 66 in the absolutely dry state, but is inferior to that of the resin in the state of equilibrium water absorption, and cannot be said to be sufficient. In addition, resin structure with poor melt retention stability, which tends to gelate and thicken during molding, and has the excellent gas barrier properties of polyketone resin, high impact resistance and thermal stability, and a highly excellent balance of properties Is further sought.

[0004]

SUMMARY OF THE INVENTION The present invention is applicable to a resin structure having high impact resistance and heat stability, particularly gas and / or liquid barrier parts, without impairing the gas barrier property of the polyketone resin. It is an object of the present invention to provide a suitable polyketone-polyethylene resin structure.

[0005]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, have found that a resin structure obtained by blending a polyketone resin and a polyolefin resin in a specific amount has a resin phase separation structure. The present inventors have found that the above-mentioned problems can be solved by controlling the dispersion structure so that the polyolefin resin phase forms a continuous phase in the molded article and the polyketone resin phase becomes a strip-shaped dispersed phase, and arrived at the present invention.

That is, the present invention relates to (1) (a) 5 to 80% by volume of a polyketone resin and (b)
A resin composition comprising 95 to 20% by volume of a polyolefin resin, and having a phase structure in which a polyolefin resin is a continuous phase and a polyketone resin is a strip-shaped dispersed phase in a resin phase separation structure observed by an electron microscope. (2) The mixing ratio of (a) the polyketone resin and (b) the polyolefin resin is 25 to 70% by volume and 75 to 3%, respectively.
0% by volume, the resin structure and the molded article according to the above (1), (3) the mixing ratio of (a) the polyketone resin and (b) the polyolefin resin is 55 to 70% by volume and 45, respectively. ~ 3
(4) (b) that the polyolefin resin is polyethylene or a copolymer containing an ethylene structural unit or a mixture containing these as a component. Features (1) to above
(3) The resin structure according to any one of (1) to (5), wherein (a) the polyketone resin comprises a polyketone polymer represented by the following general formula:
(3) The resin structure according to any of (3),

[0007]

Embedded image

(X and y are positive numbers representing the molar ratio in the polymer.) (6) R ₁ and R ₂ are different from each other and y / x is 0.01
The resin molded article for gas and / or liquid barrier parts according to the above (5), wherein (7) one means selected from injection molding, injection compression molding, and compression molding. The resin structure according to any one of the above (1) to (6), which is molded using the resin structure. (8) A container for transporting and / or storing a chemical solution or gas comprising the resin structure according to any one of the above (1) to (7) and its accessory parts. (9) A chemical liquid or gas transport and / or storage container accessory part comprising the resin structure according to any one of the above (1) to (7).

[0009]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The (a) polyketone resin used in the present invention refers to a linear alternating copolymer in which units derived from carbon monoxide and units derived from olefin are alternately arranged. Since a molded product having more excellent barrier properties can be obtained, a molded product having a repeating unit represented by the following general formula is preferably used.

[0011]

Embedded image

(X, y are positive numbers representing the molar ratio in the polymer.) In the above formula, x, y represent the molar ratio of each repeating unit in the polymer, wherein R ₁ is hydrogen and R ₂ is a methyl group. Is preferably employed. The copolymerization ratio is preferably y /
x is 0.01 to 0.10, and more preferably 0.0
It is 3 to 0.10, particularly preferably 0.05 to 0.10. By setting the content in such a range, the mechanical properties and impact strength of the obtained resin structure are further improved.

Although the molecular weight of the polyketone resin used in the present invention is not particularly limited, it was measured at 60 ° C. in m-cresol with a standard capillary viscosity measuring apparatus because the moldability and impact resistance can be improved. Intrinsic viscosity of polymer (LVN)
Is preferably 0.5 to 10.0, more preferably 0.8 to 4.0, and particularly preferably 1.5 to 2.0.

The melting point of the polyketone resin is preferably 175
C. to 300 C., more preferably 210 C. to 270 C.
° C.

For the production of the polyketone resin, a known polymerization method can be employed. For example, carbon monoxide and an olefin are converted to a palladium compound, an acid which is not hydrohalic acid and has a pKa of 6 or less measured in an aqueous solution at 18 ° C. And a contact method in the presence of a catalyst composition comprising a bidentate ligand compound of phosphorus and phosphorus, in a gas phase substantially free of a reaction diluent, or in a reaction with an alkanol (eg, methanol or ethanol). A method performed in a liquid phase containing a diluent can be adopted. In addition, a method in which the monomer is brought into contact with the catalyst composition by a method such as shaking or stirring can be exemplified.
Suitable reaction temperatures are between 20 and 150 ° C, preferably between 50 and 1 ° C.
35 ° C. Suitable reaction pressure is 100 ~ 10000k
Pa, preferably 1,000 to 10,000 kPa. After the polymerization, the polymer is recovered by decantation or filtration. The polymer may contain a residue of the catalyst composition, but if necessary, is treated and removed with a solvent or a complexing agent selective to the residue.

The palladium compound is not particularly limited as long as it is a compound containing palladium. For example, palladium acetate and palladium acetylacetonate can be used. In addition, these palladium compounds may be those supported on carbon and bonded to an ion exchanger, for example, an ion exchanger having a sulfonic acid group. The amount of the palladium compound to be used is not particularly limited, but is usually preferably 10 ^-8 to 10 ^-1 mol per mol of the total number of monomers to be polymerized.

Specific examples of non-hydrohalic acids having a pKa of 6 or less (measured in an aqueous solution at 18 ° C.) include sulfonic acid anions such as methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, And carboxylic acids such as trichloroacetic acid, difluoroacetic acid, trifluoroacetic acid, monochloroacetic acid, difluoropropionic acid, acetic acid, tartaric acid and 2,5-dihydroxybenzoic acid. Among these, p-toluenesulfonic acid and trifluoroacetic acid can be particularly preferably used. The amount of the acid having a pKa of 6 or less is preferably 0.5 to 200 equivalents, particularly preferably 1.0 to 100 equivalents, per 1 g of palladium metal atom in the catalyst composition.

The bidentate ligand compound of phosphorus to be used is not particularly limited. For example, 1,3-bis (diphenylphosphino) propane, 1,3-bis [di (2-methoxyphenyl) phosphino ] Propane, 1,4-bis (diphenylphosphino) butane, 2,3-dimethyl-
1,4-bis (diphenylphosphino) butane, 1,5
-Bis (methyl-phenyl-phosphino) pentane,
1,4-bis (dicyclohexylphosphino) butane,
1,5-bis (naphthylphosphino) pentane, 1,3
-Bis (di-p-tolylphosphino) propane, 1,4-
Bis (di-p-methoxyphenylphosphino) propane, 1,2-bis (phenylphosphino) ethene, 2,
3-bis (phenylphosphino) -2-oxapropane, 2-methyl, 2- (methyldiphenylphosphino)
-1,3-bis (diphenylphosphino) propane,
0,07-bis (diphenylphosphino) biphenyl,
1,2-bis (diphenylphosphino) benzene, 2,
3-bis (diphenylphosphino) naphthalene, 1,2
-Bis (diphenylphosphino) cyclohexane, 2,
2-dimethyl-4,5-bis (diphenylphosphino)
Dioxolane and the like. Preferably, 1,3-bis (diphenylphosphino) propane and 1,3-bis [di (2-methoxyphenyl) phosphino] propane are used. The amount of the phosphorus bidentate compound to be used is not particularly limited, but is usually 0.1 to 1 mol of the palladium compound.
-10 mol can be used, preferably 0.2-5 mol
Mol, particularly preferably 0.33 to 3 mol.

The polyolefin resin (b) used in the present invention is a polymer using an olefin as a main component of a raw material monomer, and specific examples include polyethylene, polypropylene, polystyrene, poly 1-butene, and poly 1-pentene. , A homopolymer such as polymethylpentene, an ethylene / α-olefin copolymer, a vinyl alcohol ester homopolymer, a polyolefin obtained by hydrolyzing at least a part of a vinyl alcohol ester homopolymer, [(ethylene and / or Or a copolymer of vinyl alcohol ester and propylene) obtained by hydrolyzing at least a part of [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) Copolymer],
[Polyolefin obtained by metal salification of at least a part of carboxyl groups of (copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], conjugated diene and vinyl aromatic Block copolymers with group hydrocarbons and hydrides thereof. Among them, especially polyethylene,
It is preferable to use polypropylene, a copolymerized polypropylene containing polypropylene as a main component, and an ethylene / α-olefin copolymer. Here, the polypropylene may be any one of an isotactic, atactic, and syndiotactic polypropylene or a mixture thereof. Further, a copolymerized polypropylene containing polypropylene as a main component means that the propylene component is 70%.
It is a block or a random copolymer with another olefin component containing not less than% by weight. Further, two or more kinds of polyolefin resins may be used in combination, if necessary, for post-workability such as bonding with other resins.

The melt flow rate (MFR) of the polyolefin resin is preferably from 0.1 to 70 g / 10 minutes. More preferably, it is 0.3 to 60 g / 10 minutes.
If the MFR is less than 0.1 g / 10 minutes, the fluidity is poor,
If it exceeds 70 g / 10 minutes, the impact strength may be low, which is not preferable.

In the present invention, the polyolefin resin (b) may be modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides and derivatives thereof. Alternatively, it may be prepared by heat decomposition with an organic peroxide. By using the modified polyolefin modified in this way, the compatibility is further improved, and the characteristic that the impact resistance is extremely excellent while maintaining the moldability is exhibited. Examples of compounds selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof used as a modifier include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and methylmaleic acid. , Methyl fumaric acid,
Mesaconic acid, citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride , Itaconic anhydride, citraconic anhydride, endobicyclo-
(2,2,1) -5-heptene-2,3-dicarboxylic acid, endobicyclo- (2,2,1) -5-heptene-
2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate,
Glycidyl citraconic acid and 5-norbornene
2,3-dicarboxylic acid and the like. Among them, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid, 5-norbornene-2,3-dicarboxylic acid or acid anhydrides thereof are particularly preferable.

Known methods can be used to introduce these modifiers into the olefin compound, such as copolymerizing the olefin compound and the modifier, or adding a modifier to unmodified polyolefin and graft-introducing it using a radical initiator. For example. The amount of the modifier component to be introduced is preferably in the range of 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on the entire olefin monomer in the polyolefin resin.

(B) The method for producing the polyolefin resin is not particularly limited, and any method such as radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, and coordination polymerization using a metallocene catalyst may be used. Can be.

The resin structure referred to in the present invention is defined as (b) a polyolefin resin component forming a continuous phase, and (a) a polyketone resin component having a large number of thin two-dimensionally overlapped strips (layers). Is a structure having a phase structure (laminar structure) that forms a part of or the whole. There is no particular limitation on its shape. Here, the phase structure is observed and confirmed using a scanning or transmission electron microscope.

The compounding ratio of the polyketone resin (a) and the polyolefin resin (b) in the resin structure of the present invention is 5 to 80% by volume of the polyketone resin and 95 to 20% by volume of the polyolefin resin, and is preferably. 25-70% by volume of polyketone resin, 75 of polyolefin resin
-30% by volume, more preferably 55-7% polyketone resin
0% by volume and 45 to 30% by volume of polyolefin resin. When the content of the polyketone resin (a) exceeds 80% by volume, it is difficult to form the polyolefin resin component as a continuous phase, and the object of the present invention cannot be achieved. On the other hand, if the content of the polyketone resin as the component (a) is less than 5% by volume, it is difficult to obtain a sufficient length and amount of the band-like dispersed phase of the polyketone resin component, and the object of the present invention cannot be achieved. 55-80% by volume of polyketone resin,
When the polyolefin resin is a small component, such as 45 to 20% by volume of the polyolefin resin, the polyketone resin usually forms a continuous layer. Surprisingly, the present inventors appropriately control the melt viscosity ratio between the polyketone resin and the polyolefin resin. As a result, it has been found that even if the amount of the polyolefin resin is small, a phase structure that takes a continuous phase can be formed.

The L / T (length / thickness) of the polyketone resin component forming the band-shaped dispersed phase is preferably 30 or more. More preferably, L / T is 100 or more, and particularly preferably, L / T is 150 or more. When L / T is 30 or less, it is not possible to obtain a structure that achieves a desired barrier property. The upper limit of L / T is not particularly limited, but is practically 1 × 10 ⁶ or less.

The resin structure of the present invention may contain an inorganic filler depending on the purpose and application. Such inorganic filler is not particularly limited, fibrous, plate-like,
Fillers in the form of powder or granules can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia Fibrous such as fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, whisker-like filler, mica, talc, Kaolin,
Powders of swellable layered silicates such as silica, calcium carbonate, montmorillonite, synthetic mica, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wallastenite, titanium oxide, zinc oxide, calcium polyphosphate, graphite, etc. , Granular or plate-like fillers. Among the above-mentioned inorganic fillers, glass fibers and polyacrylonitrile-based carbon fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, it can be selected from long fiber type or short fiber type chopped strand, milled fiber and the like. Further, two or more inorganic fillers can be used in combination. Further, the surface of the above-mentioned inorganic filler may be treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treating agent.

The glass fiber may be covered or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The content of the above-mentioned inorganic filler is a total amount of 1) (a) polyketone resin and (b) polyolefin resin.
The amount is preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 00 parts by weight.

The resin structure of the present invention may contain a conductive filler and / or a conductive polymer for imparting conductivity. There is no particular limitation. Examples of the conductive filler include metal powder and metal. Examples include flakes, metal ribbons, metal fibers, metal oxides, inorganic fillers coated with a conductive substance, carbon powder, graphite, carbon fibers, carbon flakes, and flaky carbon.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal species of the metal fiber include iron,
Examples thereof include copper, stainless steel, aluminum, and brass.

The metal powder, metal flake, metal ribbon and metal fiber may be subjected to a surface treatment with a surface treatment agent such as a titanate, aluminum or silane coupling agent.

Specific examples of the metal oxide include SnO ₂ (antimony doped), In ₂ O ₃ (antimony doped), Z
Examples thereof include nO (aluminum dope), and these may be subjected to a surface treatment with a surface treating agent such as a titanate, aluminum, or silane.

Specific examples of the conductive substance in the inorganic filler coated with the conductive substance include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped),
In ₂ O ₃ (antimony doping) can be exemplified. As the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanate whisker, Silicon carbide whiskers can be exemplified. As a coating method, a vacuum deposition method, a sputtering method,
Examples include an electroless plating method and a baking method. These may be surface-treated with a surface treating agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to its raw material and production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are known as the carbon powder, and can be used without any particular limitation in the present invention. In view of the above, those having an average particle size of 500 nm or less are preferable, more preferably 5 to 100 nm,
Particularly preferably, the thickness is 10 to 70 nm. The specific surface area (BET method) is preferably at least 10 m ² / g, more preferably at least 30 m ² / g.
The DBP lubrication amount is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g or more. The ash content is preferably 0.5% or less, more preferably 0.3% or less.

The carbon powder is titanate-based, aluminum-based,
Surface treatment may be performed with a surface treatment agent such as a silane coupling agent. It is also possible to use those granulated for improving the workability of the melt-kneading.

The molded resin structure of the present invention is often required to have a smooth surface. From such a viewpoint, the conductive filler has a length / diameter ratio of 200 or less in the powdery, granular, plate-like, flaky, or resin composition, as compared with the fibrous filler having a high aspect ratio, like the inorganic filler. It is preferably in any of fibrous forms.

Specific examples of the conductive polymer include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylenevinylene.

The above-mentioned conductive filler and / or conductive polymer may be used in combination of two or more kinds. Inside,
Particularly, carbon black is preferably used because of its excellent strength and cost.

Although the content of the conductive filler and / or the conductive polymer used in the present invention cannot be unconditionally defined depending on the kind of the conductive filler and / or the conductive polymer to be used, the content of the conductive filler and / or the conductive polymer is not limited. (A) polyketone resin and (b)
For a total of 100 parts by weight of the polyolefin resin, 1-2
It is preferably 50 parts by weight, more preferably 3 to
100 parts by weight.

The resin structure of the present invention has a volume resistivity of 10 ¹⁰ Ω · c in the sense of obtaining sufficient antistatic performance.
m or less. The preferred conductivity level depends on the application, but the volume resistivity is 100Ω · c.
It is preferable that the range is more than m and 10 ¹⁰ Ω · cm or less. In general, the combination of the conductive filler and the conductive polymer tends to cause deterioration in strength and fluidity. Therefore, if a target conductivity level can be obtained, it is desirable that the amount of the conductive filler and conductive polymer is as small as possible.

In the resin structure of the present invention, other components such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites and substituted products thereof, etc.) as long as the object of the present invention is not impaired. ), Weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides) , Bisurea and polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (p
-Octyl oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, non-ionics such as polyoxyethylene sorbitan monostearate) Ion-based antistatic agents, betaine-based amphoteric antistatic agents, etc.), flame retardants (eg, red phosphorus, melamine cyanurate, hydroxides such as magnesium hydroxide, aluminum hydroxide, etc., ammonium polyphosphate, brominated polystyrene, brominated) Polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or a combination of these brominated flame retardants with antimony trioxide) and other polymers can be added.

The production method is not particularly limited as long as a resin structure satisfying the requirements specified in the present invention can be obtained. However, in melt kneading, to achieve a preferable dispersion state, for example, a twin screw extruder is used. When melt-kneading, supply the polyketone resin and polyolefin resin from the main feeder, and when compounding the inorganic filler, supply from the side feeder at the tip of the extruder. A method in which additives such as an inorganic filler are mixed and melt-kneaded is exemplified.

The resin structure of the present invention may have various shapes, and a known molding method (injection molding, extrusion molding, blow molding, press molding, etc.) may be employed. It is preferable to employ one method selected from injection molding, injection compression molding, and compression molding because the object of the invention can be easily achieved. The molding temperature is usually selected from a temperature range of 5 to 50 ° C. higher than the melting point of the polyketone resin, and is generally a single layer, but may be a multilayer structure by a method such as a two-color molding method. Absent.

Here, the multilayer structure means a structure having the resin structure of the present invention in at least one layer thereof. The arrangement of each layer is not particularly limited, and all the layers may be formed of the resin structure of the present invention, or the other layers may be formed of another thermoplastic resin. In the case of two layers, the layer composed of the resin structure of the present invention is preferably the innermost layer in order to sufficiently exhibit the permeation resistance effect.

The thermoplastic resin used as the other layer includes saturated polyester, polysulfone, polyethylene tetrafluoride, polyetherimide, polyamideimide, polyamide, polyketone copolymer, polyphenylene ether, polyimide, polyethersulfone, and polyether. Ketone, polythioetherketone, polyetheretherketone, thermoplastic polyurethane, polyolefin, A
Examples thereof include BS, polyamide elastomer, polyester elastomer, and the like, and a mixture thereof or various additives may be used.

The resin structures of the present invention can be bonded or welded to each other or to other molded products. The method is not particularly limited, and a known technique can be used.

The resin structure of the present invention is, for example, Freon-1
1, Freon-12, Freon-21, Freon-22, Freon-113, Freon-114, Freon-115, Freon-134a, Freon-32, Freon-123, Freon-
124, Freon-125, Freon-143a, Freon-
141b, Freon-142b, Freon-225, Freon-C318, R-502, 1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil base Brake fluid, glycol ether brake fluid, borate ester brake fluid, brake fluid for extreme cold, silicone oil brake fluid,
Mineral oil brake fluid, power steering oil, window washer fluid, gasoline, methanol, ethanol,
Isoptanol, butanol, nitrogen, oxygen, hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium, xenon, excellent barrier properties against gas and / or liquid or vaporized gas such as pharmaceutical agents, For example, various gas bottles such as the above-mentioned gas and / or liquid barrier films, air bags, shampoos, rinses, liquid soaps, detergents, chemical liquid storage tanks, gas storage tanks, cooling liquid tanks, oil transfer For tank,
Automobile parts such as disinfectant tanks, blood transfusion pump tanks, fuel tanks, washer liquid tanks, oil reservoir tanks, medical equipment parts, and general life equipment parts tanks, bottle-shaped molded articles, or those tanks and bottles Valves and fittings such as cut-off valves attached, gauges for attached pumps, parts such as cases, fuel filler under pipes, various fuel tubes such as ORVR hoses, reserve hoses, vent hoses, connection parts (connectors, etc.), oil Tubes and connection parts, brake hoses and connection parts, nozzles and hoses for window washer fluid, cooler hoses and connection parts for cooling water and refrigerant, air conditioner refrigerant tubes and connection parts, floor heating pipes and connection parts,
Hose for fire extinguishers and fire extinguishing equipment, tubes for medical cooling equipment and connecting parts and valves, tubes for transporting chemicals and gases, containers for storing chemicals, etc., where chemicals and gas permeability are required, Starting with mechanical parts such as automotive parts, internal combustion engine applications, power tool housings, etc.
Electric and electronic parts such as calculators, acoustic parts, electric fan parts, vacuum insulation boards such as refrigerators and cool boxes, medical, food, household and office supplies, building materials related parts such as wallpaper, furniture parts, other gas bags, balloons, It is effective for various uses such as airships.

[0050]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples. (1) Alcohol gasoline permeability A die for forming a tube at the tip of an extruder having a diameter of 40 mm, a sizing die for cooling and controlling the size of the tube,
A tube having an outer diameter of 8 mm and an inner diameter of 6 mm was formed using a take-up machine. Then put two tubes
The tube was cut to a length of 0 cm, one end of the tube was sealed, and 6 g of an alcohol gasoline mixture obtained by mixing commercially available regular gasoline and ethanol in a 75:25 weight ratio was precisely weighed and charged inside, and the other end was also sealed. Thereafter, the entire weight was measured, and the test tube was placed in an explosion-proof oven at 40 ° C., treated for 500 hours, and the reduced weight was measured. (2) Oxygen permeability GTR- according to JIS K7126 A method (differential pressure method)
10 (manufactured by Yanako Kagaku Kogyo). (3) Material properties Measured according to the following standard methods. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod impact strength: ASTM D256 (4) Observation of phase-separated structure A tube molded product is freeze-cut along the flow direction (MD direction) of the molten resin, and the cut surface is cut. Observation was performed using a transmission electron microscope (TEM). (5) Melt viscosity ratio Using a plunger type capillary rheometer (manufactured by Toyo Seiki Seisaku-sho, Ltd., Capillograph type 1C), the melt viscosity (poise) at a melt kneading temperature and a shear rate of 10 sec ^-1 described in each example was measured. It was determined by the following equation. (Melting viscosity ratio) = (Melting viscosity of polyketone resin) / (Melting viscosity of polyolefin resin) (6) Melt viscosity increase ratio during melt residence Melt kneading temperature described in each example in the capillary rheometer used in the above (5). And the melt viscosity (poise) at a shear rate of 10 seconds @ ^{-1 at} 250 DEG C. was measured and determined by the following equation. (Melting retention viscosity increase ratio) = (Melting viscosity after 30 minutes retention processing) / (Melting viscosity before retention processing)

The polyolefins used in the examples and comparative examples are as follows. <Polyolefin resin> A commercially available polyethylene resin was used. The properties of each resin are as follows. (PE-1): High density polyethylene (MFR = 1.5,
Density 0.954). (PE-2): High density polyethylene (MFR = 5, density 0.968). (PE-3): ethylene / 1-hexene copolymer (MF
R = 4, density 0.920).

REFERENCE EXAMPLE 1 Preparation of polyketone copolymer (PK-1): 0.1 mmol of palladium acetate, 0.15 mmol of 1,3-bis [(di (2-methoxyphenyl) phosphino] propane) were used as catalyst compositions. 2 mmol of trifluoroacetic acid was weighed and placed in a 250 ml pressure-resistant autoclave.
Then, the inside of the autoclave was replaced with carbon monoxide,
Ethylene at a pressure of 00 kPa, propylene at a pressure of 140 kPa, and carbon monoxide at a pressure of 3000 kPa were charged into the autoclave and reacted at 90 ° C. for 1 hour. After the reaction was completed, the autoclave was cooled, and then the polymer (PK-1) in the autoclave was taken out. The obtained polymer was dissolved in m-cresol and a small amount of deuterated dimethyl sulfoxide by heating to 90 ° C., and 90 MHz 1H-N
When the molar ratio of x and y was measured by MR, y / x =
LVN measured at 60 ° C. in m-cresol with a polymer of 0.070, melting point 220 ° C. was 1.8 dl / g. The melting point was measured using DSC-7 manufactured by PERKIN-ELMER under a nitrogen atmosphere in a sample amount of 10 m.
g, the top value of the peak observed when the temperature was measured from −100 ° C. to 20 ° C./min was defined as the melting point of the polymer.

Reference Example 2 Preparation of polyketone copolymer (PK-2): 0.1 mmol of palladium acetate, 0.15 mmol of 1,3-bis [(di (2-methoxyphenyl) phosphino] propane) were used as the catalyst composition. 2 mmol of trifluoroacetic acid was weighed and placed in a 250 ml pressure-resistant autoclave.
Then, the inside of the autoclave was replaced with carbon monoxide,
Ethylene at a pressure of 00 kPa, propylene at a pressure of 140 kPa, and carbon monoxide at a pressure of 3000 kPa were charged into the autoclave and reacted at 90 ° C. for 3 hours. After the reaction was completed, the autoclave was cooled, and then the polymer (PK-2) in the autoclave was taken out. When the molar ratio of x and y of the obtained polymer was measured, y / x = 0.0
72, melting point: 221 ° C., LVN: 2.8 dl / g
Met.

Examples 1 to 4 and Comparative Examples 1 and 2 The polyketone resin and the polyolefin resin produced in Reference Example 1 or Reference Example 2 were mixed in the amounts shown in Table 1 and biaxially extruded with a TEX30 model manufactured by Nippon Steel Works. Supplied from the main feeder of the machine, kneading temperature 250 ° C, screw rotation speed 200r
Melt kneading was performed at pm. After drying the obtained pellets,
Injection molding (IS100FA manufactured by Toshiba Machine Co., mold temperature 80
C) to prepare test pieces. Table 1 shows the results of measurement of the phase separation structure, permeation resistance, material strength, and the like of each sample.

Comparative Example 3 A test piece was prepared from PK-1 by injection molding (IS100FA, manufactured by Toshiba Machine Co., mold temperature: 80 ° C.). Table 1 shows the results of measuring the permeability resistance, material strength, and the like of each sample.

Comparative Example 4 A test piece was prepared from PE-1 by injection molding (IS100FA manufactured by Toshiba Machine Co., mold temperature 40 ° C.). Table 1 shows the results of measuring the permeability resistance, material strength, and the like of each sample.

[0057]

[Table 1]

The resin structure of the present invention having a specific phase-separated structure from Examples 1 to 4 and Comparative Examples 1 to 4 has good permeation resistance, and has a particularly good balance of impact resistance and thermal stability. It turns out that it is an excellent thing of high practical value.

[0059]

The resin structure of the present invention has good gas and / or liquid barrier properties, good impact properties, and excellent thermal stability, so that it can be suitably used for various applications. For example, it is suitable for electrical / electronic related equipment, precision machine related equipment, office equipment, automobile / vehicle related parts, building materials, packaging materials, furniture, daily necessities and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // B29K 23:00 B29K 73:00 73:00 B29L 22:00 B29L 22:00 B65D 1/00 A F Term (Reference) 3E033 BA13 BA14 BA15 CA01 CA07 CA16 CA20 FA01 FA02 4F204 AA03K AA04 AA49K AG07 AH55 FA01 FB01 FF01 4F206 AA03K AA49K AE10 AH55 JA07 JF01 4J002 BB03X BB04X BB12X BB16X010

Claims (9)

[Claims] 1. A resin composition comprising (a) 5 to 80% by volume of a polyketone resin and (b) 95 to 20% by volume of a polyolefin resin, wherein the polyolefin resin is continuous in a resin phase separation structure observed by an electron microscope. A resin structure having a phase structure in which the phase and the polyketone resin are strip-shaped dispersed phases. 2. The resin structure according to claim 1, wherein the mixing ratio of (a) the polyketone resin and (b) the polyolefin resin is 25 to 70% by volume and 75 to 30% by volume, respectively. 3. The resin structure according to claim 1, wherein the mixing ratio of (a) the polyketone resin and (b) the polyolefin resin is 55 to 70% by volume and 45 to 30% by volume, respectively. 4. The polyolefin resin (b) is polyethylene or a copolymer containing an ethylene structural unit or a mixture containing these components.
4. The resin structure according to any one of items 1 to 3. 5. The resin structure according to claim 1, wherein (a) the polyketone resin comprises a polyketone polymer represented by the following general formula. Embedded image (X and y are positive numbers representing the molar ratio in the polymer.) 6. The resin structure according to claim 5, wherein R ₁ and R ₂ are different from each other, and y / x is 0.01 to 0.10. 7. Molding is performed by using one of injection molding, injection compression molding, and compression molding.
The resin structure according to any one of the above. 8. A container for transporting and / or storing a chemical or gas comprising the resin structure according to claim 1. 9. An accessory for a container for transporting and / or storing a chemical or gas, comprising the resin structure according to claim 1. Description: