JP2003128056A - Multi-layer hollow container with barrier property and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a multi-layer hollow container with barrier property and its manufacturing method that is excellent in flexibility for container design, barrier property, inter-layer bonding ability, and mechanical characteristics. SOLUTION: The multi-layer hollow container comprises a barrier layer composed of (a) polyolefin resin, (b) polyamide resin, (c) liquid crystalline resin and/or (d) resin composition composed of layer-state silicate and a thermoplastic resin layer composed of (e) other thermoplastic resins than the resin compositions constituting the barrier layer, and is a barrier multi-layer hollow container characterized in that it contains, in one part therein, a fuse-bonding part whose strength is 60% or more of that of the non-fuse-bonding part.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a multilayer hollow container having excellent barrier properties, mechanical properties and productivity, and a method for producing the same. In particular, a specific barrier property obtained by controlling a resin composition composed of a polyolefin resin, a polyamide resin, a liquid crystalline resin and / or a layered silicate so as to have a specific phase structure, excellent mechanical properties, and heat welding property. The present invention relates to a barrier multi-layer hollow container having a barrier layer having post-processability and the like, and a method for producing the same.

[0002]

Polyolefin resins such as polyethylene and polypropylene are widely used as the most general plastics for daily sundries, toys, machine parts, electric / electronic parts and automobile parts. However, in recent years, resin products that are required to have gas barrier properties (permeation resistance) for the purpose of preventing leakage of contents and preventing entry of outside air in order to ensure safety, storage stability, and environmental pollution prevention properties It is increasing. Among them, for automobile fuel tanks, etc., the switch from metal to plastic is being actively considered because of its lightness, ease of molding, flexibility in design, and ease of handling, but safety is being considered. , Storage stability, further prevent leakage of contents to ensure environmental pollution prevention,
It is important to prevent the entry of outside air, and a material having permeation resistance is required. However, polyolefin containers such as polyethylene and polypropylene are the most common plastic containers, but their range of use is often restricted due to insufficient barrier properties against gasoline and certain oils. , The improvement is desired.

A barrier multi-layer hollow container typified by such a resin fuel tank is a barrier resin such as HDPE / adhesive layer / polyamide or EVOH in view of barrier properties and mechanical properties required for the hollow container. / Adhesive layer / HDPE
An example of a multilayer blow-molded article consisting of 5 layers of 3 types is given. However, in multi-layer blow molding, in addition to the lack of flexibility in container design, there are problems such as large burrs occurring during molding in terms of productivity, long molding cycle, lack of uniform wall thickness, etc. there were.

On the other hand, in many fields of industrial parts including automobile parts, the injection molding method is widely used for molding resins because of its good workability and economical efficiency. However, in products such as fuel tanks that require high fuel barrier properties and mechanical properties, barrier properties and impact resistance of multi-layer hollow containers with barrier properties can be achieved even when conventional thermoplastic resin materials are normally injection molded. There is a problem in that it is difficult to develop various properties such as properties in a well-balanced manner.

As described above, there is a demand for a multilayer hollow container having good freedom in container design, productivity, barrier properties, and mechanical properties, which is an alternative to conventional multilayer blow molding, and a manufacturing method thereof.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a barrier multi-layer hollow container having good container design flexibility, productivity, barrier properties and mechanical properties, and a method for producing the same.

[0007]

The inventors of the present invention have conducted studies to achieve the above object, and as a result, obtained by forming a layer having a specific dispersion structure by multicolor injection molding and then joining the layers. The present inventors have found that the container to be used is a method for producing a barrier-type multi-layer hollow container that overcomes the problems, and arrived at the present invention.

That is, the present invention provides (1) (a) polio
Refin resin, (b) polyamide resin and (c) liquid crystal
Resin and / or (d) layered silicate resin set
Forming a barrier layer (e) barrier layer formed of a composition
Resin made of a thermoplastic resin other than the resin composition
A multi-layer hollow container having a fat layer, which is a part of the hollow container
The welded part has a strength of 50% or more of the non-welded part
Barrier multi-layer hollow container characterized by being (2)
  (A) polyolefin resin, (b) polyamide resin,
From (c) liquid crystalline resin and / or (d) layered silicate
The barrier layer formed by the resin composition
When the thickness in the direction perpendicular to the
As a phase structure observed with a microscope, the thickness direction from the surface to the inside
(A) The polyolefin resin has a continuous phase toward the layer
(B) Polyamide resin as the dispersed phase, (b) Poly
Amide resin is a continuous phase and (a) polyolefin resin is
Is the phase dispersed part, (a) is the polyolefin resin a continuous phase?
(B) Sequential observation of areas where the polyamide resin is the dispersed phase
Described in (1) above, which is a barrier layer
(3) (a) Polyolefin
Resin, (b) polyamide resin, (c) liquid crystalline resin
And / or (d) a resin composition comprising a layered silicate
The barrier layer is formed in the direction perpendicular to the surface of the molded product.
And the total thickness from the surface of the resin molded product to 5
(A) Polyolefin tree at any depth of 10%
Continuous phase with fat and (b) dispersed phase with polyamide resin
Is observed, and 45 to 55% of the total thickness from the surface
(B) Polyamide resin
Observing continuous phase and dispersed phase of (a) polyolefin resin
Described in (2) above, which is a barrier layer
(4) (a) Polyolefin
Resin, (b) polyamide resin, (c) liquid crystalline resin
And / or (d) a resin composition comprising a layered silicate
The barrier layer is formed in the direction perpendicular to the surface of the molded product.
And the phase observed in the resin molded product with an electron microscope.
As a structure, from the surface to the inner layer in the thickness direction (a)
Both polyolefin resin and (b) polyamide resin are connected.
The continuous phase, (b) the polyamide resin is the continuous phase and
(A) A portion where the polyolefin resin is a dispersed phase, (a)
Both polyolefin resin and (b) polyamide resin are connected.
The part that becomes the succession phase is a barrier layer that is observed sequentially.
A barrier multi-layer hollow container according to (1) above,
(5) (a) Polyolefin resin, (b) Polyamide
Resin, (c) liquid crystalline resin and / or (d) layered silicic acid
Molded barrier layer made of salt resin composition
When the thickness is measured in the direction perpendicular to the product surface,
From the surface to an arbitrary depth of 5 to 10% of the total thickness
(A) polyolefin resin and (b) polyamide resin
Both fats are observed as a continuous phase, and the total thickness from the surface
At any depth of 45-55% to (b) poly
Amide resin continuous phase and (a) polyolefin resin
Is a barrier layer in which a dispersed phase is observed.
(6) A barrier multi-layer hollow container according to (4) above
  Said (a) polyolefin resin and (b) polyamid
The higher temperature of the melting point of the resin is Tp (° C)
Temperature, Tp + 10 ℃ ~ Tp + 100 ℃ at any temperature
And the melt viscosity ratio defined by the following equation (1) is
200 seconds ^-10.5 or more at any of the following shear rates
Under, and shear rate 1000 seconds^-1Any of the above
If the shear rate is 0.8 or more,
(1) to (5), which is a rear layer
A barrier multi-layer hollow container according to any of the above,

[0009]

[Formula 3]

(7) The barrier multi-layer hollow according to any one of (1) to (6) above, wherein the thermoplastic resin other than the resin composition forming the barrier layer (e) is a polyolefin. Container, (8) Any one of the above (1) to (7), characterized in that it is welded by at least one method selected from injection welding, hot plate welding, vibration welding, heat ray welding and laser welding. (9) The barrier multi-layer hollow container according to any one of (1) to (8) above, which has one or more openings formed of barrier layer components. , (10)
(A) polyolefin resin, (b) polyamide resin,
(C) a barrier layer formed of a resin composition containing a liquid crystalline resin and / or (d) a layered silicate; and (e) a thermoplastic resin layer formed of a thermoplastic resin other than the resin composition forming the barrier layer. A method for producing a multi-layer hollow container having the above-mentioned multi-layer hollow container, wherein two or more divided bodies constituting the multi-layer hollow container are laminated and formed by multicolor injection molding, and subsequently the obtained divided bodies are joined to each other. (11) (a) polyolefin resin, (b) polyamide resin, (c), wherein the strength of the welded portion forming the container is 50% or more of that of the non-welded portion. A phase observed in an electron microscope in a resin molded product when the barrier layer formed of a resin composition composed of a liquid crystalline resin and / or (d) a layered silicate has a thickness in a direction perpendicular to the surface of the molded product. As a structure A part where (a) the polyolefin resin is the continuous phase and (b) the polyamide resin is the dispersed phase from the surface to the inner layer in the thickness direction, (b) the polyamide resin is the continuous phase and (a) the polyolefin resin is the dispersed phase. The barrier multi-layer hollow container according to the above (10), characterized in that a barrier layer is formed in which a portion, (a) a polyolefin resin in a continuous phase and (b) a polyamide resin in a dispersed phase are sequentially observed. Manufacturing method, (12) A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is perpendicular to the surface of the molded article. (A) a continuous phase of a polyolefin resin and (b) a polyphase resin at an arbitrary depth of 5 to 10% of the total thickness from the surface of the resin molded product, where Dispersed phase due to amide resin was observed, and from the surface to the total thickness 45
The barrier property according to (11) above, wherein a barrier layer in which (b) a continuous phase of a polyamide resin and (a) a dispersed phase of a polyolefin resin are observed is formed at an arbitrary depth of 55%. Method for producing multilayer hollow container, (13) (a) polyolefin resin, (b) polyamide resin, (c) liquid crystalline resin and / or (d) molded barrier layer formed from resin composition composed of layered silicate When the thickness in the direction perpendicular to the product surface is taken as the phase structure observed in the resin molded product with an electron microscope, both (a) polyolefin resin and (b) polyamide resin are directed from the surface to the inner layer in the thickness direction. The part that becomes the continuous phase,
To form a barrier layer in which (b) a portion where the polyamide resin is a continuous phase and (a) a portion where the polyolefin resin is a dispersed phase, and (a) a portion where the polyolefin resin and (b) the polyamide resin are both a continuous phase are sequentially observed. A method for producing the barrier multi-layer hollow container according to (10) above,
(14) A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is oriented in a direction perpendicular to the surface of the molded article. In terms of thickness, (a) a polyolefin resin and (b) a polyamide resin are both observed as a continuous phase at an arbitrary depth of 5 to 10% from the surface in the resin molded product, and the surface is From the above (13), a barrier layer in which (b) a continuous phase of a polyamide resin and (a) a dispersed phase of a polyolefin resin are observed at an arbitrary depth of 45 to 55% of the total thickness is formed. (15) The method for producing a barrier multi-layer hollow container according to (15), wherein the melt viscosity ratio defined by the following formula (1) at the temperature during the molding process has a shear rate of 200 seconds.
^-0.5 or less at any shear rate of ^-1 or less,
Further, (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and // which has a shear rate of 0.8 or more at an arbitrary shear rate of 1000 sec- ¹ or more.
Alternatively, (d) a method for producing a barrier multi-layer hollow container according to any one of the above (10) to (14), which comprises melt-molding a resin composition comprising a layered silicate.

[0011]

[Formula 4]

(16) (a) Polyolefin resin,
From a thermoplastic resin other than (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a resin composition comprising a layered silicate and (e) a resin composition forming a barrier layer. (10), wherein the thermoplastic resin layer is formed by two-color injection molding.
(15) A method for producing a barrier multi-layer hollow container according to any one of (15), (17) a method in which a divided body obtained by multicolor injection molding is injection-welded, hot-plate welded, vibration-welded, heat-ray welded, or laser-welded. The above (10) to (1) are characterized in that they are bonded to each other by at least one selected welding method.
(6) The method for producing a barrier multi-layer hollow container according to any one of (6) and (18) the welding method for joining the divided bodies obtained by multicolor injection molding to each other is injection welding and / or vibration welding. (17) The method for producing a barrier multi-layer hollow container according to (17) above, (19) One or more openings formed of barrier layer components are formed by multicolor injection molding. ) To (18), the method for producing the barrier multi-layer hollow container is provided.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

The polyolefin resin (a) used in the present invention is a thermoplastic resin obtained by polymerizing or copolymerizing olefins such as ethylene, propylene, butene, isoprene and pentene. Specific examples include polyethylene, polypropylene, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, poly 1-butene,
Homopolymers such as poly-1-pentene and polymethylpentene, ethylene / α-olefin copolymers, vinyl alcohol ester homopolymers, polymers obtained by hydrolyzing at least a part of vinyl alcohol ester homopolymers, [Polymer obtained by hydrolyzing at least a part of copolymer of (ethylene and / or propylene) and vinyl alcohol ester], [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated polymer) Saturated carboxylic acid ester)], [(ethylene and / or propylene) with (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) Copolymer], a block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, and
A hydride of the block copolymer or the like is used.

Among them, polyethylene, polypropylene, ethylene / α-olefin copolymer, [copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [ A copolymer obtained by metallizing at least a part of the carboxyl group of the copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) is preferable.

The ethylene / α-olefin copolymer referred to herein is a copolymer of ethylene and at least one or more α-olefin having 3 to 20 carbon atoms, and has the above-mentioned 3 to 20 carbon atoms. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-
Decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene,
3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1- Pentene, 4-ethyl-1-hexene, 3-
Ethyl-1-hexene, 9-methyl-1-decene, 11
-Methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof. These α
Among the olefins, a copolymer using an α-olefin having 3 to 12 carbon atoms is preferable from the viewpoint of improving mechanical strength. This ethylene / α-olefin copolymer is α-
The olefin content is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and further preferably 3 to 20 mol%.

Furthermore, 1,4-hexadiene, dicyclopentadiene, 2,5-norbornadiene, 5-ethylidenenorbornene, 5-ethyl-2,5-norbornadiene, 5- (1'-propenyl) -2-norbornene and the like At least one kind of conjugated diene may be copolymerized.

The unsaturated carboxylic acid used in the [copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)] is acrylic acid or methacrylic acid. Or a mixture thereof, and examples of the unsaturated carboxylic acid ester include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester and the like of these unsaturated carboxylic acids. ,
Alternatively, a mixture thereof may be mentioned, but a copolymer of ethylene and methacrylic acid, and a copolymer of ethylene, methacrylic acid and acrylic acid ester are particularly preferable.

Among these polyolefin resins, low,
Medium and high density polyethylene, polypropylene, ethylene / α-olefin copolymers are preferred. More preferred are low density, medium density and high density polyethylene, and particularly preferred is high density polyethylene having a density of 0.94 to 0.97 g / cm ³ .

Melt flow rate of the (a) polyolefin resin of the present invention (hereinafter abbreviated as MFR .: ASTM D
1238) is preferably 0.01 to 70 g / 10 minutes, more preferably 0.03 to 60 g / 10 minutes. If the MFR is less than 0.01 g / 10 minutes, the fluidity is poor, and if it exceeds 70 g / 10 minutes, the impact strength may be lowered depending on the shape of the molded product, which is not preferable.

The method for producing the (a) polyolefin resin used in the present invention is not particularly limited, and radical polymerization,
Any method such as coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, or coordination polymerization using a metallocene catalyst can be used.

Further, in the present invention, it is preferable that a part or all of the (a) polyolefin resin is modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. When the modified polyolefin resin is used, the compatibility is improved, the controllability of the phase separation structure of the obtained resin composition is improved, and as a result, the excellent barrier property is exhibited, which is one of the preferred embodiments. is there.

Examples of unsaturated carboxylic acids or their derivatives used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methylfumaric acid, mesaconic acid,
Citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itacone, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, Methacrylic acid 2
-Ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconic acid, 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 acid anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, Examples thereof include glycidyl itaconate, glycidyl citracone, and 5-norbornene-2,3-dicarboxylic acid. Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid and maleic anhydride are particularly preferable.

The method of introducing these unsaturated carboxylic acid or its derivative component into the polyolefin resin is not particularly limited, and the olefin compound as the main component and the unsaturated carboxylic acid or its derivative compound are copolymerized in advance, or an unmodified polyolefin is used. A method such as introducing an unsaturated carboxylic acid or a derivative compound thereof into the resin by performing a grafting treatment using a radical initiator can be used. The amount of the unsaturated carboxylic acid or its derivative component introduced is preferably 0.001 to 40 mol%, more preferably 0.01 to 40% by mol based on the whole olefin monomer in the modified polyolefin.
It is suitable to be in the range of ˜35 mol%.

The (b) polyamide resin used in the present invention is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main constituent components. Typical examples of its main components are 6-aminocaproic acid, 1
Amino acids such as 1-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine and nonamethylenediamine. , Undecamethylenediamine, dodecamethylenediamine, 2,
2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( Aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis Aliphatic, alicyclic and aromatic diamines such as (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalate Acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid Aliphatic, alicyclic, and aromatic dicarboxylic acids such as tarric acid, 5-methylisophthalic acid, 5-sodiumsulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or higher and excellent in heat resistance and strength, and specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecane amide (nylon 1)
1), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6/6)
T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66/6
T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66/6
I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T
/ 6/6), polyhexamethylene terephthalamide / polydodecane amide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), poly Xylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T),
Examples include polynonamethylene terephthalamide (nylon 9T) and mixtures thereof.

Particularly preferred polyamide resins are nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T.
/ 12, and copolymers having hexamethyleterephthalamide units such as nylon 6T / 6 copolymer, and these polyamide resins can be used according to the required properties such as impact resistance, moldability and compatibility. It is also suitable for practical use as a mixture.

The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is 1.5 to 7.
Although those having a range of 0 can be used, a relative viscosity of 3.0 to particularly for forming a specific phase-dispersed structure and developing toughness.
The range of 6.0 is preferable. In order to control the degree of polymerization of these polyamide resins, compounds such as monocarboxylic acids, dicarboxylic acids, monoamines and diamines may be added during the polymerization, and the resulting amino group / carboxyl group balance of the polyamide resin may change. However, in the present invention, either an amino group-rich polyamide or a carboxyl group-rich polyamide can be used and can be appropriately selected.

A copper compound is preferably used in the polyamide resin of the present invention in order to improve long-term heat resistance. Specific examples of the copper compound, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and the aforementioned inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole , Benzimidazole and other complex compounds. Of these, monovalent copper compounds, especially monovalent copper halide compounds, are preferable, and cuprous acetate, cuprous iodide and the like can be exemplified as particularly preferable copper compounds. The addition amount of the copper compound is usually 0.0 with respect to 100 parts by weight of the polyamide resin.
It is preferably 1 to 2 parts by weight, and further 0.015
It is preferably in the range of 1 to 1 part by weight. If the added amount is too large, metallic copper will be liberated during melt molding, and coloring will reduce the value of the product. In the present invention, it is also possible to add an alkali halide in the form of being used in combination with a copper compound. Examples of this alkali halide compound include:
Mention may be made of lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide, with potassium iodide and sodium iodide being particularly preferred.

In the resin composition used for the barrier layer of the present invention, the blending ratio of the polyolefin resin as the component (a) and the polyamide resin as the component (b) is preferably 20 to 80% by weight of the polyolefin resin and 80 to 20 of the polyamide resin.
% By weight. More preferably, polyolefin resin 3
0 to 70% by weight and 70 to 30% by weight of polyamide resin. Particularly preferred are 40 to 60% by weight of polyolefin resin and 60 to 40% by weight of polyamide resin. (A)
When the content of the polyolefin resin is more than 80% by weight, it becomes difficult for the polyamide resin component, which is a feature of the barrier layer of the present invention, to form a continuous phase, and it is difficult to achieve the object of the present invention. Further, if the content of the polyolefin resin as the component (a) is less than 20% by weight, the toughness and the adhesiveness of the barrier layer are deteriorated, which is not preferable.

In the present invention, a conventionally known compatibilizing agent may be contained for the purpose of improving the compatibility of the component (a) polyolefin resin and the component (b) polyamide resin. At this time, if a compatibilizing agent based on a modified polyolefin resin is used as one of the components of the (a) polyolefin resin as the compatibilizing agent, the compatibility as the property of the (a) polyolefin resin is improved, and (b) the polyamide resin. Adhesion with, compatibility with and stability of the phase separation structure as the resulting resin molding is improved, resulting in excellent impact resistance,
Permeation resistance is exhibited, which is one of the preferable embodiments.

Examples of such a compatibilizer include the above-mentioned (a)
As one example of the component of the polyolefin resin, an acid-modified polyolefin obtained by introducing an unsaturated dicarboxylic acid anhydride by a grafting treatment using a radical initiator, an ethylene / unsaturated carboxylic acid copolymer, or an α, β-unsaturated Examples thereof include an epoxy group-containing olefin-based copolymer having a glycidyl ester of a saturated acid as a main constituent, and two or more kinds of these can be used simultaneously.

The unsaturated dicarboxylic acid anhydride used for the acid-modified polyolefin includes maleic anhydride, itaconic anhydride, citraconic anhydride, and maleic anhydride is particularly preferable. The unsaturated carboxylic acid used in the ethylene / unsaturated carboxylic acid copolymer may be acrylic acid, methacrylic acid, or a mixture thereof, and may partially contain unsaturated carboxylic acid ester.

The content of the compatibilizing agent is preferably 0.5 to 50% by weight of the polyolefin resin (a). More preferably 1 to 40% by weight, particularly preferably 1
~ 30% by weight.

A characteristic feature of the barrier layer of the present invention is that (a) a polyolefin resin component forms a continuous phase (matrix phase) and (b) a polyamide resin component forms a dispersed phase (for example, a sea-island structure, FIG. 1). ) Is 5 relative to the total thickness from the surface when the thickness in the direction perpendicular to the surface of the barrier layer.
10%, preferably 5 to 20%, particularly preferably 5 to
Observed and confirmed using scanning and transmission electron microscopy at any depth of 25%. The phase structure portion formed on the surface portion of the barrier layer is particularly preferable because it has an excellent balance of moldability, adhesiveness with other resins, and toughness. If the phase structure portion formed on the surface of the molded product is not observed at an arbitrary depth of 5 to 25% with respect to the total thickness from the surface, the resin molded product of the present invention is characterized by high adhesiveness and toughness. It becomes difficult to express the above, and the object of the present invention cannot be achieved. Further, if the phase structure portion is observed at an arbitrary depth exceeding 25% of the total thickness from the surface, the barrier property of the resin molded product and the mechanical strength are deteriorated, which is not preferable.

The polyamide resin component (b), which is a feature of the barrier layer of the present invention, forms a continuous phase (matrix phase),
(A) The phase structure in which the polyolefin resin component forms a dispersed phase (for example, a sea-island structure, FIG. 2) has a thickness of 4 relative to the total thickness from the surface when the direction perpendicular to the surface of the barrier layer is taken as the thickness.
It is observed and confirmed using a scanning electron microscope and a transmission electron microscope at an arbitrary depth of 5 to 55%, preferably 40 to 60%, and particularly preferably 30 to 70%. The phase structure portion formed in the central portion of the barrier layer has an excellent balance of barrier properties and mechanical strength, and is particularly preferable.
Unless the phase structure portion formed in the center of the molded article is observed at an arbitrary depth of 30 to 70% of the total thickness from the surface, the barrier layer of the present invention exhibits high barrier properties. Becomes difficult and the object of the present invention cannot be achieved. Further, if the phase structure portion is observed at an arbitrary depth deviating from 30 to 70% with respect to the total thickness from the surface, the toughness and adhesiveness of the barrier layer are deteriorated, which is not preferable.

The phase structure (for example, sea-sea structure, FIG. 3) in which the (a) polyolefin resin component and (b) polyamide resin component together form a continuous phase (matrix phase), which is a feature of the barrier layer of the present invention, is When the thickness in the direction perpendicular to the surface of the barrier layer is taken, the total thickness from the surface is 5 to 10
%, Preferably 5 to 20%, particularly preferably 5 to 25%
Are observed and confirmed using scanning and transmission electron microscopes at any depth. The phase structure portion formed on the surface portion of the barrier layer is particularly preferable because it has an excellent balance of moldability, adhesiveness with other resins, and toughness. If the phase structure portion formed on the surface portion of the barrier layer is not observed at any depth of 5 to 25% with respect to the total thickness from the surface, the high adhesion and toughness characteristic of the barrier layer of the present invention can be obtained. It becomes difficult to express, and the object of the present invention cannot be achieved. Further, if the phase structure portion is observed at an arbitrary depth exceeding 25% of the total thickness from the surface, the barrier property of the resin molded product and the mechanical strength are deteriorated, which is not preferable.

The barrier layer of the present invention comprises (1) a phase structure in which the polyolefin resin component is the continuous phase and the polyamide resin component is the dispersed phase (FIG. 1), and (2) the polyamide resin component is the continuous phase and the polyolefin resin component. When the phase structure in which is a dispersed phase (FIG. 2) and (3) the phase structure in which the polyolefin resin component and the polyamide resin component are both continuous phases (FIG. 3) is the thickness in the direction perpendicular to the surface of the barrier layer, A molded product in which the phase structure is formed in the order of phase structure (1) / phase structure (2) / phase structure (1) and phase structure (3) / phase structure (2) / phase structure (3) in the thickness direction. Is. The phase structures (1), (2) and (3) are observed and confirmed using a scanning electron microscope and a transmission electron microscope.

Further, the shape of the barrier layer is not particularly limited, and there are cases where the dispersed phase and the continuous phase of the polyolefin resin appear multiple times in various places of the barrier layer. This phase structure is observed and confirmed using a scanning electron microscope and a transmission electron microscope.

The barrier layer of the present invention can be obtained, for example, by the following method.

That is, the barrier layer of the present invention is generally formed by melt molding, but in melt molding, a temperature difference and a stress difference are likely to occur between the resin surface layer and the inside of the resin when flowing. In the present invention, this is positively utilized, and resins (a) polyolefin resin and (b) polyamide resin having different dependences of melt viscosity on shear rate are used, and the shear rate of the shear rate generated in the resin surface layer and inside the resin is Due to the difference, on the one hand, (a) the part where the polyolefin resin becomes the continuous phase is produced, and on the other hand (b) the part where the polyamide resin becomes the continuous phase is produced, or either (a) or (b) Can also generate a continuous phase part. For example, taking injection molding as an example, when molding at a certain molding processing temperature, a shear rate at that temperature is 200 seconds.
^-The melt viscosity ratio (where,
The melt viscosity ratio is defined as the melt viscosity of polyamide resin / melt viscosity of polyolefin resin. ) Is 0.5 or less, the polyamide resin forms a continuous phase. On the other hand, since the shear rate increases in the surface layer of the barrier layer due to friction with the mold, these resins have a melt viscosity ratio of 0.8 at a shear rate of about 1000 sec ^-1 or more at the same temperature. With the above combination, the polyolefin resin can be used as the continuous phase in the surface layer portion.

As is apparent from the above, the main point of the first stage is to explain the embodiment of the present invention utilizing the shear stress dependence of the melt viscosity ratio, and the present invention is limited to specific melt viscosity ratios. Moreover, since the shear stress generated at an arbitrary position of the barrier layer can be manipulated by the mold design or the like, it can be easily understood that such a phase structure also occurs at an arbitrary position.

The liquid crystal resin (c) used in the present invention is a resin capable of forming an anisotropic melt phase, and preferably has an ester bond. For example, a liquid crystalline polyester comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, etc., and forming an anisotropic melt phase, Alternatively, it is a liquid crystalline polyesteramide which is composed of the structural unit and a structural unit selected from an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit and the like, and which forms an anisotropic molten phase.

Examples of aromatic oxycarbonyl units include p-hydroxybenzoic acid and 6-hydroxy-2-
Examples of the structural unit and aromatic dioxy unit generated from naphthoic acid include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t -Structural units and aromatics formed from butyl hydroquinone, phenyl hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, etc. Examples of the aliphatic dicarbonyl unit and / or terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4 ′
-Diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'diphenyletherdicarboxylic acid acid,
Structural unit generated from adipic acid, sebacic acid, etc., ethylene glycol as the alkylenedioxy unit,
The structural unit produced from 1,3-propylene glycol, 1,4-butanediol, etc. (among others, the structural unit produced from ethylene glycol is preferable), and the aromatic iminooxy unit is produced from, for example, 4-aminophenol. Examples of the structural unit include

Specific examples of the liquid crystalline polyester include p
, A liquid crystalline polyester consisting of structural units formed from hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, structural units formed from p-hydroxybenzoic acid, 6
A structural unit formed from hydroxy-2-naphthoic acid,
A liquid crystalline polyester comprising a structural unit produced from an aromatic dihydroxy compound and / or an aliphatic dicarboxylic acid, a structural unit produced from p-hydroxybenzoic acid,
A liquid crystalline polyester comprising a structural unit produced from 4,4′-dihydroxybiphenyl, a terephthalic acid and / or an aliphatic dicarboxylic acid such as adipic acid and sebacic acid, and a structural unit produced from p-hydroxybenzoic acid , A structural unit produced from ethylene glycol, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol,
Liquid crystalline polyester composed of structural units derived from terephthalic acid and isophthalic acid, structural unit derived from p-hydroxybenzoic acid, structural unit derived from ethylene glycol, structural unit derived from 4,4′-dihydroxybiphenyl, terephthalic acid And / or a liquid crystalline polyester comprising a structural unit produced from an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, an aromatic dihydroxy compound A liquid crystalline polyester comprising a structural unit and a structural unit formed from an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid can be used.

Among the examples of the liquid crystalline polyester which forms the anisotropic molten phase, the following (I), (II) and (III) are listed.
And a liquid crystalline polyester comprising the structural units of (IV),
Alternatively, a liquid crystalline polyester comprising the structural units (I), (III) and (IV) is preferably exemplified.

Particularly preferred is a liquid crystalline polyester comprising structural units (I), (II), (III) and (IV).

[0048]

[Chemical 1]

(However, R ₁ in the formula is

[0050]

[Chemical 2]

[0051] represents one or more groups selected from, R ₂ is

[0052]

[Chemical 3]

One or more groups selected from are shown below. However, in the formula, X represents a hydrogen atom or a chlorine atom. ) The structural unit (I) is a structural unit formed from p-hydroxybenzoic acid, and the structural unit (II) is 4,4′-dihydroxybiphenyl, 3,3 ′, 5,5′-tetramethyl-
4,4'-dihydroxybiphenyl, hydroquinone,
t-butyl hydroquinone, phenyl hydroquinone,
Methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4'-
A structural unit produced from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether,
Structural unit (III) is a structural unit produced from ethylene glycol, structural unit (IV) is terephthalic acid, isophthalic acid,
4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,
Each of the structural units formed from one or more aromatic dicarboxylic acids selected from 4'-diphenyl ether dicarboxylic acid is shown. Of these, R ₁

[0054]

[Chemical 4]

And R ₂ is

[0056]

[Chemical 5]

Particularly preferred are:

The liquid crystalline polyester which can be preferably used in the present invention is, as described above, structural units (I) and (II
Copolymer consisting of I) and (IV) and the structural unit
One or more selected from the copolymers consisting of (I), (II), (III) and (IV), and the structural units (I), (II) and (III)
The copolymerization amounts of (IV) and (IV) are arbitrary. However, in order to exert the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II), (I
II), in the case of a copolymer consisting of (IV), the structural unit (I)
And (II) are the structural units (I), (II) and (III)
30 to 95 mol% is preferable relative to the total of 40 to 8
5 mol% is more preferable. The structural unit (III) is 70 to 5 relative to the total of the structural units (I), (II) and (III).
Mol% is preferable, and 60 to 15 mol% is more preferable.
Also, the molar ratio of structural unit (I) to (II) [(I) / (II)]
Is preferably 75/25 to 95/5, and more preferably 78/22 to 93/7. Also, the structural unit (IV)
Is preferably substantially equimolar to the total of structural units (II) and (III).

On the other hand, when the structural unit (II) is not contained, the structural unit (I) is the structural unit (I) from the viewpoint of fluidity.
It is preferably 40 to 90 mol%, particularly preferably 60 to 88 mol%, with respect to the total of (III), and the structural unit (IV) is substantially equimolar to the structural unit (III). Preferably there is.

The term "substantially equimolar" means that the units constituting the polymer main chain excluding the terminals are equimolar, but the units constituting the terminals are not necessarily equimolar.

As the liquid crystalline polyesteramide,
Polyesteramides forming an anisotropic melt phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferable.

The liquid crystalline polyester and the liquid crystalline polyesteramide which can be preferably used are 3,3′-diphenyldicarboxylic acid and 2,2′-diphenyl in addition to the components constituting the structural units (I) to (IV). Aromatic dicarboxylic acids such as dicarboxylic acids, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl sulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4′-dihydroxybenzophenone and 3,4′-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, 1 To the extent that liquid crystallinity is not impaired by aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol and aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, 2,6-hydroxynaphthoic acid and p-aminobenzoic acid. Further copolymerization can be carried out within the range.

The method for producing the above-mentioned (c) liquid crystalline resin used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method.

For example, in the production of the liquid crystalline polyester, the following production method is preferably mentioned. (1) Diacylated aromatic dihydroxy compounds such as p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl and diacetoxybenzene, and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a deacetic acid condensation polymerization reaction. (2) p-hydroxybenzoic acid and an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with acetic anhydride. Then, after acylating the phenolic hydroxyl groups, a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl ester of p-hydroxybenzoic acid and aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl and hydroquinone, and diphenyl ester of aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid A method for producing a liquid crystalline polyester by a dephenol polycondensation reaction. (4) p-Hydroxybenzoic acid and aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid are reacted with a predetermined amount of diphenyl carbonate to form diphenyl esters, respectively,
A method for producing a liquid crystalline polyester by adding an aromatic dihydroxy compound such as 4,4′-dihydroxybiphenyl or hydroquinone and performing a dephenol polycondensation reaction. (5) Liquid crystal by the method of (1) or (2) in the presence of polyester polymer such as polyethylene terephthalate, oligomer or bis (β-hydroxyethyl) ester of aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate. Of producing water-soluble polyester.

The melt viscosity of (c) the liquid crystalline resin is not particularly limited, but in order to further exert the effect of the present invention,
The value measured at the melting point of the liquid crystalline resin + 10 ° C is 100 Pa
It is preferably s or less, more preferably 0.1
It is 50 Pa · s, and most preferably 0.5 to 30 Pa · s. The melt viscosity here is 1,000 at a shear rate.
Nozzle diameter 0.5mmφ, nozzle length 10mm under the condition of (1 / sec)
It is the value measured by a Koka type flow tester using the nozzle.

Here, the melting point is Tm1 + 20 ° C. after the observation of the endothermic peak temperature (Tm1) observed when the temperature of the polymerized polymer is measured at a temperature rise rate of 20 ° C./min in the differential calorimetry. 2 minutes after holding for 5 minutes
After cooling to room temperature under the condition of 0 ° C / min, once again,
The endothermic peak temperature (Tm2) observed when measured under a temperature rising condition of 0 ° C / min is the melting point.

The compounding ratio of the (c) liquid crystalline resin used in the present invention is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the total of (a) polyolefin resin and (b) polyamide resin. %, Particularly preferably 1.5 to 10% by weight.

The liquid crystal resin (c) is (a) a polyolefin resin phase and (b) a polyamide resin if the relationship between the phase structure of the (a) polyolefin resin and the (b) polyamide resin satisfies the requirements of the present invention. Although it may be present in any of the phases, the presence of the (b) polyamide resin phase is preferred because the barrier layer of the present invention can achieve a well-balanced high barrier property and high adhesiveness.

The layered silicate (d) used in the present invention is formed by stacking an octahedral sheet containing an element selected from aluminum, magnesium, lithium and the like with a tetrahedral silicic acid sheet to form one plate crystal layer. It has a 2: 1 type structure and has exchangeable cations between the layers of the plate crystal layer. The size of the single plate crystal is usually 0.05 to 0.5 μm in width and 6 to 15 Å in thickness. The cation exchange capacity of the exchangeable cation is 0.2 to 3 meq / g, and the cation exchange capacity is preferably 0.8 to 1.5 meq / g.

Specific examples of the layered silicate include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite and sauconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyaite, zirconium phosphate and titanium phosphate. Examples thereof include swelling mica such as Li-type fluoro-teniolite, Na-type fluoro-teniolite, Na-type tetra-silicon-fluorine mica, and Li-type tetra-silicon-fluorine mica, which may be natural or synthetic. .. Among these, smectite clay minerals such as montmorillonite and hectorite, and swelling synthetic mica such as Na-type tetrasilicon fluoromica and Li-type fluoroteniolite are preferable.

The layered silicate of the present invention is preferably a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions.

Examples of the organic onium ion include ammonium ion, phosphonium ion and sulfonium ion. Among these, ammonium ion and phosphonium ion are preferable, and ammonium ion is particularly preferably used. As ammonium ion,
Any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

Examples of primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium and benzyl ammonium.

Examples of the secondary ammonium ion include methyldodecyl ammonium and methyl octadecyl ammonium.

Examples of the tertiary ammonium ion include dimethyldodecyl ammonium and dimethyl octadecyl ammonium.

Examples of the quaternary ammonium ion are benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium and the like, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium. , Alkyl trimethyl ammonium ions such as trimethyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didodecyl ammonium,
Examples thereof include dimethyldialkylammonium ions such as dimethyldioctadecyl ammonium.

In addition to these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-An ammonium ion derived from aminododecanoic acid and the like are also included.

Among these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid and the like are preferable.

The layered silicate in which the exchangeable cations existing between the layers in the present invention are exchanged with the organic onium ions are:
It can be produced by reacting a layered silicate having an exchangeable cation between layers and an organic onium ion by a known method. Specific examples thereof include a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or molten ammonium salt.

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined from the viewpoint of the dispersibility of the layered silicate, the thermal stability during melting, the suppression of the generation of gas and odor during molding, and the like. 0.4 for cation exchange capacity
The range is from 2.0 to 2.0 equivalents, preferably 0.8 to 1.2 equivalents.

These layered silicates are used after being pretreated with a coupling agent such as an isocyanate type compound, an organic silane type compound, an organic titanate type compound, an organic borane type compound and an epoxy compound in addition to the above organic onium salt. You may.

A preferred coupling agent is an organic silane compound, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysisilane and β- (3,4- Epoxy cyclohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ
-Ureidopropyltrimethoxysilane, γ- (2-
Ureidoethyl) alkoxide compound containing ureido group such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyl Isocyanato group-containing alkoxysilane compounds such as diethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyl Amino group-containing alkoxysilane compounds such as dimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyl Ropyltrimethoxysilane,
Hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ
Examples include carbon-carbon unsaturated group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and hydrochloride. Particularly, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used.

Treatment of the layered silicate with these coupling agents is carried out in a polar solvent such as water, methanol or ethanol.
Or a method of adsorbing the coupling agent to the layered silicate in these mixed solvents, or a method of dropping the coupling agent solution while stirring the layered silicate while stirring the layered silicate in a high-speed stirring mixer such as a Henschel mixer, Furthermore, any method may be used in which the silane coupling agent is directly added to the layered silicate, and the mixture is adsorbed by mixing in a mortar or the like. When the layered silicate is treated with a coupling agent,
It is preferable to mix water, acidic water, alkaline water and the like at the same time in order to accelerate the hydrolysis of the alkoxy group of the coupling agent. In addition to water, water such as methanol or ethanol and an organic solvent that dissolves both coupling agents may be mixed in order to increase the reaction efficiency of the coupling agent. The reaction can be further promoted by heat-treating the layered silicate treated with such a coupling agent. A so-called integral blending method may be used in which these coupling agents are added when the layered silicate and the thermoplastic polyester are melt-kneaded without previously treating the layered silicate with the coupling agent.

The order of the treatment of the layered silicate with the organic onium ion and the treatment with the coupling agent is not particularly limited, but it is preferable to first treat with the organic onium ion and then with the coupling agent.

In the present invention, the content of the (d) layered silicate is 100 in total of the polyamide resin and the polyolefin resin.
The amount of inorganic ash is 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, and particularly preferably 1.5 to 10 parts by weight.
The range is parts by weight. If the ash content is too small, the barrier property improving effect is small, and if the ash content is too large, the toughness may decrease. The amount of inorganic ash is 500 ° C for 2 g of the resin composition.
It is a value obtained by ashing for 3 hours in the electric furnace.

Further, (d) the layered silicate is (a) a polyolefin resin phase and (b) a polyamide resin if the relationship between the phase structure of the (a) polyolefin resin and the (b) polyamide resin satisfies the requirements of the present invention. Although it may be present in any of the phases, the presence of the (b) polyamide resin phase is preferred because it can achieve the well-balanced high barrier property and high adhesiveness which are the characteristics of the barrier layer of the present invention.

If necessary, the resin composition used for the barrier layer of the present invention may contain an inorganic filler other than the layered silicate. The inorganic filler is not particularly limited, but fibrous, plate-like, powdery, granular, etc. fillers can be used. Specifically, for example, glass fiber,
PAN-based or pitch-based carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers,
Asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers and other fibrous, whisker-like fillers, Mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons,
Examples thereof include powdery, granular or plate-like fillers such as clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite. In the filler, glass fiber and PAN-based carbon fiber are preferably used when conductivity is required. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing a resin, and for example, long fiber type or short fiber type chopped strands, milled fiber and the like can be selected and used. Further, the above-mentioned fillers can be used in combination of two or more kinds. The surface of the above-mentioned filler used in the present invention may be treated with a known coupling agent (eg, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agent. .

Further, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or the like, or a thermosetting resin such as an epoxy resin or the like.

The amount of the above-mentioned filler added is 0.5 to 200 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total amount of the polyamide resin and the polyolefin resin.
The amount is 0 parts by weight, more preferably 10 to 100 parts by weight.

The above-mentioned inorganic filler is added in a total amount of 100 parts (a) polyolefin resin and (b) polyamide resin.
It is preferably 200 parts by weight or less with respect to parts by weight. Preferably 1 to 200 parts by weight, particularly preferably 5 to
It is in the range of 150 parts by weight.

In the resin composition used for the barrier layer of the present invention, other components may be added within a range that does not impair the effects of the present invention.
For example, antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substitution products thereof), weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), Molding agents and lubricants (montanic acid and its metal salts, their esters, their 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 (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkylsulfate-type anionic antistatic agents) Agent,
Quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (eg red phosphorus, melamine cyanurate, water) Magnesium oxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or a combination of these brominated flame retardants and antimony trioxide, etc.), Other polymers can be added.

The method for obtaining the resin composition used for the barrier layer in the present invention is not particularly limited as long as the phase structure required by the present invention can be obtained, and a generally known melt-kneading method can be mentioned. Above all, the melt-kneading method using a single-screw or twin-screw extruder is preferable as a simple and efficient production method. For example, when a filler-added system is melt-kneaded with a twin-screw extruder, polyamide resin and liquid crystalline resin and /
Alternatively, a method in which a layered silicate is supplied and a polyolefin resin is supplied from a side feeder at the tip of an extruder, or a polyamide resin and a liquid crystalline resin and / or a layered silicate are melt-kneaded and then melt-kneaded with a polyolefin resin. A method can also be mentioned as a preferable embodiment.

The thermoplastic resin used in the thermoplastic resin layer composed of a thermoplastic resin other than the resin composition forming the barrier layer (e) of the present invention has a phase structure or composition different from the requirements of the present invention. Composed of plastic resin. The type of the thermoplastic resin is not particularly limited and can be appropriately selected depending on the purpose of use of the resin molded product. Specific examples thereof include polyolefin resin, thermoplastic polyester resin, polysulfone resin, tetrafluoropolyethylene resin, polyetherimide resin, polyamideimide resin, polyamide resin, polyimide resin, polycarbonate resin, polyethersulfone resin, polyetherketone resin. , Polythioether ketone resin, polyphenylene sulfide resin, polyether ether ketone resin, thermoplastic polyurethane resin, ABS resin, polyamide elastomer, polyester elastomer and the like, and these may be used as a mixture of two or more kinds. Above all, the above-mentioned polyolefin resins are more preferably used, and low-, medium- and high-density polyethylene, polypropylene, ethylene / α-olefin copolymers and acid-modified products thereof are particularly preferably used. In addition, impact resistance of these thermoplastic resins,
It is also practically preferable to use the mixture as a mixture within a range that does not impair the effects of the present invention, depending on the required properties such as moldability and barrier properties.

In the multilayer hollow container of the present invention, an adhesive layer may be appropriately formed between the barrier layer and the thermoplastic resin layer for the purpose of further improving the impact resistance and moldability of the container and the adhesive force between the layers. Is preferred. The adhesive resin (f) that constitutes the adhesive layer is not particularly limited as long as it exhibits adhesiveness to the barrier layer and the thermoplastic resin layer and is capable of multicolor molding with these. Specific examples include α-olefins such as ethylene and propylene and α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and crotonic acid, their esters, anhydrides, halides and sodium. , Modified polyolefins such as random, block and graft copolymers with at least one compound selected from derivatives such as salts with potassium, magnesium, zinc and the like, α-olefins such as ethylene and propylene and vinyl acetate, Vinyl alcohol
Random, block, and graft copolymers with at least one compound selected from the group consisting of styrene and styrenes, copolyamide adhesives, copolyester adhesives, and the like. Among these adhesive layers, the degree of crystallinity measured by the X-ray diffraction method is 50% or less, preferably 40 to 0%, and 0.01 to 10% by weight of the graft-treated unsaturated carboxylic acid or its derivative. A modified polyolefin containing 0.05 to 3% by weight is preferable, and when the amount of unsaturated carboxylic acid or its derivative and the crystallinity are within the above ranges, a laminated structure having particularly excellent adhesiveness to the barrier layer is obtained. The body is obtained. Examples of the preferred unsaturated carboxylic acid or its derivative used here include the series of compounds exemplified as the modifier of the polyolefin component of the component (a), among which unsaturated compounds such as acrylic acid and methacrylic acid are preferred. Dicarboxylic acid anhydrides such as dicarboxylic acid, maleic anhydride, itaconic anhydride,
Glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate are preferred.

The modified polyolefin may be a single type or a mixture of two or more types. Two
In the case of a mixture of one or more kinds, the crystallinity and the graft amount of the mixture may be within the above range, and the graft-modified polyolefin having the crystallinity and / or the graft amount outside the above range and / or the graft-unmodified A polyolefin may be included.

Suitable examples of the polyolefin before or without graft modification include homopolymers of α-olefins having 2 to 20 carbon atoms or copolymers of two or more kinds. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene and 1-octadecene. The polyolefin may be copolymerized with a small amount of a monomer other than α-olefin, for example, 10 mol% or less.

Particularly preferable examples of the polyolefin include ethylene homopolymers and ethylene / α-olefin random copolymers. Specifically, linear low density polyethylene (L-LDPE), ethylene / propylene copolymer, ethylene / butene copolymer and the like can be mentioned. Among these, especially MFR is 0.1 to 50 g.
/ 10 min, preferably 0.2 to 20 g / 10 mi
n, the density is 0.850 to 0.940 g / cm ³ , preferably 0.855 to 0.920 g / cm ³ , and the ethylene content is 30 to 95 mol%, preferably 40 to 92 mol%,
The crystallinity measured by X-ray diffractometry is 50% or less, preferably 40% or less.

The modified polyolefin used as the adhesive layer may contain a tackifier. Specific examples thereof include aliphatic hydrocarbon resins, alicyclic hydrocarbon resins obtained by hydrogenating aromatic hydrocarbon resins, α-pinene resins, terpene resins, rosins, modified rosins and mixtures thereof. As the tackifying resin, a solid amorphous polymer which has been conventionally used as an adhesive or an adhesive in the fields of adhesive tapes, paints and hot melt adhesives is used. Among them, the softening point (ring and ball method) is 105 to 150 ° C, preferably 110 to 140 ° C.
And an alicyclic hydrocarbon having a hydrogenation rate to the aromatic nucleus of 80% or more, preferably 85% or more is particularly preferable.
A commercially available product may be used as the adhesion-imparting agent. For example, "Arcon P-125" manufactured by Arakawa Chemical Industries, Ltd. may be mentioned.

The blending ratio of the modified polyolefin and the tackifier is 99 to 60% by weight of the modified polyolefin, preferably 95 to 80% by weight, and the tackifier is 1 to 40% by weight, preferably 5 to 20% by weight.

The barrier multi-layer hollow container of the present invention is shown in FIG.
As shown in 6, a barrier layer 4 made of (a), (b), (c) and / or (d) and a thermoplastic resin layer 5 made of (e), and an adhesive layer made of (f), if necessary. After forming two or more laminated divided bodies 2 and 3 which form a multilayer hollow container by using them, respectively, the laminated divided bodies are welded to each other to form the barrier multi-layer hollow container 1.

In the barrier multi-layer hollow container 1 of the present invention, the strength of the welded portion 6 when the divided bodies 2 and 3 are welded to each other is 60% or more of the strength of the non-welded portion, preferably 70. %
That is all. When the strength of the welded portion is less than 60%, the mechanical strength of the hollow container is insufficient and the toughness is deteriorated, which is not preferable.

The barrier multi-layer hollow container 1 of the present invention is shown in FIG.
As shown in (1), it has one or more openings 7 formed of the resin composition component of the barrier layer 4 composed of (a), (b), (c) and / or (d). Constituting the opening with the barrier layer component is a preferable mode because it is possible to suppress the permeation and leakage of the contents from the opening.

As shown in FIGS. 4 to 6, the method for producing a barrier multi-layer hollow container according to the present invention comprises the steps (a), (b) and (c) described above.
And / or a barrier layer 4 made of (d) and a thermoplastic resin layer 5 made of (e), and if necessary, an adhesive layer made of (f) are laminated by two or more forming a multi-layer hollow container by multicolor injection molding. It comprises an injection molding step of molding each of the divided bodies 2 and 3 and a joining step of forming the barrier multi-layer hollow container 1 by welding the laminated divided bodies formed in the injection molding step to each other.

The multicolor injection molding used in the injection molding step which is the manufacturing method of the present invention is two-color (2 materials) or three-color (3 materials) injection molding and injection compression molding. It is possible to mold a split body forming a three-layer hollow container from three layers and three colors. For example, in the case of two-color injection molding, molding is performed using two injection devices and two sets of molds. As a primary molding, a thermoplastic resin layer composed of (e) is injection molded, the obtained thermoplastic resin layer is moved to a mold for secondary molding, and then as a secondary molding, (a), (b), (C)
A barrier layer composed of and / or (d) can be injection-molded on the thermoplastic resin layer to obtain a hollow container divided into two layers of the thermoplastic resin layer and the barrier layer. Also,
In the case of three-color injection molding, a three-layer hollow container divided body having an adhesive layer between the thermoplastic resin layer and the barrier layer is obtained in the same manner as above using three injection devices. You can

The welding method used in the joining step which is the manufacturing method of the present invention includes injection welding, hot plate welding, vibration welding,
Heat wire welding and laser welding can be mentioned, and the step of welding the joint surfaces of the divided bodies of the hollow container can be performed, for example, as follows.

In the case of the injection welding method, after the divided body is inserted into the mold or the position of the divided body is changed, the joint surfaces are held together and a molten resin is newly added to the periphery of the joint. By injection, the divided bodies are welded to each other to form a hollow container. The injection welding conditions at this time may be normal conditions, for example, a resin temperature of 230 to 320 ° C., an injection pressure of 10 to 150 MPa, a mold clamping force of 100 to 4000 tons, and a mold temperature of 30 to 150 ° C. (In addition, the method of changing the position in the mold described above is
It is also called die slide molding or die rotation molding).

In the case of the hot plate welding method, the joint surfaces of the divided bodies are melted by the hot plate, and the joint surfaces of the divided bodies are quickly brought into pressure contact with each other for welding. The hot plate conditions at this time may be normal conditions. For example, in the case of the contact method, the hot plate temperature 230
˜350 ° C. and melting time of 20 to 60 seconds can be adopted.

In the case of the vibration welding method, the joint surfaces of the divided bodies are pressed against each other in the vertical direction, and in this state, they are welded by frictional heat generated by vibrating laterally. The vibration conditions at this time may be normal conditions, for example, a vibration frequency of 100 to 300 Hz and an amplitude of 0.5 to 2.0 mm can be adopted.

In the case of the hot wire welding method, for example, the iron-chromium wire rod is embedded in the joint portion of the split body, the joint surfaces are pressure-welded to each other, an electric current is applied to the wire rod to generate Joule heat, and the joint surface is generated by the heat generation. Weld.

In the case of the laser welding method, a laser beam non-absorptive split body and a laser beam absorptive split body are superposed at the joint surface, and the laser beam is applied from the non-absorptive split body side. For welding (see, for example, FIG.
6, the divided body 2 is a laser beam non-absorbent, and the divided body 3
As the laser light absorbing property, and the laser light is irradiated from the divided body 2 side). Further, in order to make it laser light absorbing, a method of adding carbon black can be mentioned. By adding carbon black, the transmittance of the irradiated laser light can be made 5% or less, and the energy of the laser light can be efficiently converted into heat. The laser welding conditions at this time may be ordinary conditions. For example, as the laser light, a YAG laser, a laser light wavelength of 800 to 1060 nm, and a laser light output of 5 to 30 W can be adopted.

Among the welding methods used in these joining steps, injection welding and vibration welding are particularly preferable from the viewpoint of strength of the welded portion and moldability.

The barrier multi-layer hollow container produced by such a multicolor injection molding and welding method has excellent barrier properties, mechanical properties, heat welding properties, and moldability. And / or it can be preferably used as a hollow container for gas storage. Examples of the chemical liquid or gas include CFC-11, CFC-12, CFC-21, CFC-22, CFC-113, CFC-1.
14, CFC-115, CFC-134a, CFC-3
2, Freon-123, Freon-124, Freon-12
5, Freon-143a, Freon-141b, Freon-1
42b, Freon-225, Freon-C318, R-50
2,1,1,1-Trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil-based brake fluid, glycol ether brake fluid, borate ester brake fluid , Brake fluid for cold regions, silicone oil type brake fluid, mineral oil type brake fluid, power steering oil, window washer fluid, gasoline, methanol, ethanol, isoptanol, butanol, nitrogen, oxygen, hydrogen, carbon dioxide, methane, propane, Examples of the gas and / or liquid include natural gas, argon, helium, xenon, and pharmaceutical agents. Due to their excellent resistance to permeation of chemicals and / or gases, for example, bottles for various chemicals such as shampoos, rinses, liquid soaps, detergents, chemical storage tanks, gas storage tanks, coolant tanks, oil transfer Liquid tank, antiseptic tank, blood pump tank, fuel tank, canister,
Examples thereof include automobile parts such as washer fluid tanks and oil reservoir tanks, medical equipment parts, tanks as general household appliance parts, bottle-shaped molded articles, and various tanks.

[0114]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples. (1) Degree of freedom in design Whether or not it was easy to change the wall thickness part of the hollow container and to install the opening was checked, and those that could be easily changed and installed by modifying the mold during molding were judged to be acceptable. Those that require post-processing that are not easily changed are rejected. (2) Barrier property Fig. 4 obtained by the multicolor injection molding and welding method of the present invention
The model gasoline (toluene // isooctane = 50 /) of 50% of the internal volume in the multilayer hollow container (internal volume: about 400 cc, thermoplastic resin layer thickness: 3 mm, barrier layer thickness: 2 mm, opening diameter: 3 mm) (/ 50% by volume) and ethanol were mixed at a ratio of 90 to 10 by weight, and the barrier property was evaluated from the weight loss behavior when the opening was closed and the mixture was treated at 60 ° C. for 500 hours.
The fuel reduction amount of less than 0.8 g / day was determined to be acceptable. It is unacceptable if the amount of fuel reduction is 0.8 g / day or more. (3) Interlayer adhesiveness Water is added to the multilayer hollow container up to 50% and dropped from a height of 2 m onto a concrete floor to form a barrier layer and a thermoplastic resin layer. The presence or absence of peeling at the interface was observed, and those that did not peel were judged to have passed interlayer adhesion. Those separated at the interface are rejected. (4) Strength of welded portion The welded portion 6 having a width of 10 mm shown in FIG.
The test piece 8 having the above and the test piece 9 of the non-welded portion were cut out and the tensile strength was measured, and those having a welded portion strength of 60% or more of the non-welded portion were judged to be acceptable. A weld strength of less than 60% is unacceptable. (5) Observation of Phase Separation Structure of Barrier Layer (Phase Separation Structure) Surface layer portion of 0.1 to 0.2 mm (5 to 10%) from the surface in the thickness direction of the barrier layer having a thickness of 2 mm of the multilayer hollow container. And the central part 0.9 to 1.1 mm (45 to 55%) from the surface was observed using an electron microscope (TEM, SEM). (6) Melt viscosity ratio Plunger type capillary rheometer (“Capirograph” type 1C manufactured by Toyo Seiki Seisaku-sho, Ltd.) was used, and shear rates at 280 ° C. were 100 sec ⁻¹ and 5000.
The melt viscosity (Pa · s) at second ⁻¹ was measured and determined by the following formula (1).

[0115]

[Formula 5]

Reference Example 1 Each polyolefin resin, polyamide resin, liquid crystalline resin and layered silicate resin are as follows. Unless otherwise specified, all were prepared by polymerizing according to a known method. <Polyolefin resin: PO and its manufacturing method> (a-1): MFR 0.03 g / 10 minutes and high density polyethylene of density 0.956 by a conventional method, (a-2): MFR 6 g / 10 minutes and density of 0.956. High density polyethylene, (a-3): MFR 0.6 g / 10 min, density 0.956
100 parts by weight of high density polyethylene, maleic anhydride 1
Parts by weight and 0.1 parts by weight of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane are mixed and melt-extruded at a cylinder temperature of 230 ° C. using a twin-screw extruder to obtain modified polyethylene. It was (A-4): MFR 6 g / 10 minutes, 100 parts by weight of high-density polyethylene having a density of 0.956, 1 part by weight of maleic anhydride, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane 0 1 part by weight was mixed and melt-extruded using a twin-screw extruder at a cylinder temperature of 230 ° C. to obtain modified polyethylene. (A-5): MFR 0.04 g / 10 minutes, density 0.95
6, 100 parts by weight of high-density polyethylene, 1 part by weight of maleic anhydride, 2,5-dimethyl-2,5-di (tert-
Butylperoxy) hexane 0.1 part by weight is mixed, and 2
A modified polyethylene was obtained by melt extrusion using a shaft extruder at a cylinder temperature of 230 ° C. <Polyamide resin> (b-1): Nylon 6 resin having a melting point of 225 ° C and a relative viscosity of 2.35. (B-2): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.75. (B-3): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 4.40. <Liquid-Crystalline Resin> 901 parts by weight of p-hydroxybenzoic acid,
126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 346 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 884 parts by weight of acetic anhydride were equipped with a stirring blade and a distillation pipe. Aromatic oxycarbonyl units of 7
2.5 molar equivalents, aromatic dioxy units 7.5 molar equivalents,
Melting point 265 ° C., 275, which is composed of 20 molar equivalents of ethylenedioxy units and 27.5 molar equivalents of aromatic dicarboxylic acid units.
Melt viscosity at 13 ℃ ・ Pa (orifice 0.5φ × 10m
m, shear rate 1,000 (1 / sec) liquid crystalline resin (c
-1) was obtained. <Layered silicate> Na-type montmorillonite (Kunimine industry: Kunipia F, cation exchange capacity 120 meq / 10
0 g) 100 g was stirred and dispersed in 10 liters of warm water, and 48 g of trioctylmethylammonium chloride was added thereto.
2 L of warm water in which (the same amount as the cation exchange capacity) was dissolved was added and stirred for 1 hour. The generated precipitate was filtered off and washed with warm water. This washing and filtering operation was repeated 3 times, and the obtained solid was vacuum dried at 80 ° C. to obtain a dried layered silicate (d
-1) was obtained. When the amount of inorganic ash of this layered silicate was measured, the proportion of inorganic ash was 67% by weight. The inorganic ash content is a value obtained by ashing 0.1 g of layered silicate in an electric furnace at 500 ° C. for 3 hours. <Manufacturing Method of Resin Composition for Barrier Layer> The polyamide resin, the liquid crystalline resin and / or the layered silicate having the composition shown in Table 1 are mixed and supplied from the main feeder of a TEX30 twin-screw extruder manufactured by Japan Steel Works. Then, after melt-kneading at a kneading temperature of 270 ° C. and a screw rotation speed of 200 rpm, the obtained kneaded product and the polyolefin resin were melt-kneaded at a kneading temperature of 250 ° C. and a screw rotation speed of 200 rpm using the same extruder. The obtained pellets were dried to obtain a resin composition (B-1 to B-7) for the barrier layer.

Example 1 HDPE (“HIZEX”, 8200B, manufactured by Mitsui Chemicals, Inc.) was used for the primary molding in the injection molding process, and the materials shown in Table 1 were used to prepare the thermoplastic resin layer portion shown in FIG. Injection molding (resin temperature: 230 ° C, mold temperature: 40 ° C),
Then, as a secondary molding, the resin composition B-1 for the barrier layer is formed.
Injection molding of the barrier layer using (resin temperature: 280 ° C,
Mold temperature: 80 ° C.) to obtain a two-layer molded article of the hollow container divided body having the shape shown in FIG. Also,
In the same manner, a split two-layer molded product of FIG. 6 was also obtained.

Next, as a joining step, the divided body 2 shown in FIGS.
Vibration welding method for layered products (frequency: 270 Hz, amplitude:
The joining surfaces were welded together at a pressure of 1.5 mm and a pressure of 10 MPa to obtain the hollow container shown in FIG. The properties of the obtained hollow container were evaluated by the above-mentioned methods. The results are shown in Table 2.
Shown in.

Example 2 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-2 for the barrier layer was used. The results are shown in Table 2.

Example 3 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-3 for the barrier layer was used. The results are shown in Table 2.

Example 4 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-4 for the barrier layer was used. The results are shown in Table 2.

Example 5 A hollow container was obtained in the same manner as in Example 1 except that the injection welding method (resin for welding: B-1, resin temperature: 300 ° C., mold temperature: 80 ° C.) was used in the joining step. . The results are shown in Table 2.

Example 6 Carrying out except that the hot plate welding method (hot plate temperature: 320 ° C., melting time: 30 seconds, holding pressure: 0.1 MPa) was used in the bonding step with the resin composition B-4 for the barrier layer. A hollow container was obtained in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 HDPE (“HIZEX”, 8 manufactured by Mitsui Chemicals, Inc.) was used as the outer layer.
200B), and a hollow container was manufactured by multilayer blow molding using B-1 as the inner layer. The properties of the obtained hollow container were evaluated by the above-mentioned methods. The results are shown in Table 3.

Comparative Example 2 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-5 for the barrier layer was used. The results are shown in Table 3.

Comparative Example 3 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-6 for the barrier layer was used. The results are shown in Table 3.

Comparative Example 4 A hollow container was obtained in the same manner as in Example 1 except that the resin composition B-7 for the barrier layer was used. The results are shown in Table 3.

[0128]

[Table 1]

[0129]

[Table 2]

[0130]

[Table 3]

From the examples 1 to 6 and the comparative examples 1 to 4, a barrier layer having a specific phase-separated structure and a thermoplastic resin layer were subjected to multicolor injection molding to form a two-layer molded product of a hollow container divided body. The barrier multi-layer hollow container obtained by the method of the present invention in which it is welded at the joint surface was excellent in the degree of freedom in shape, the barrier property and the interlaminar adhesiveness, and was of excellent practical value.

[0132]

The barrier multi-layer hollow container obtained by the method of the present invention has a degree of freedom of shape which cannot be obtained by conventional blow molding, and allows the polyolefin resin and the polyamide resin to form a specific phase structure. It has a specific barrier property obtained by the above, an excellent interlayer welding property, and the like.

[Brief description of drawings]

FIG. 1 is a model diagram of a phase structure in which (a) a polyolefin resin component forms a continuous phase and (b) a polyamide resin component forms a dispersed phase.

FIG. 2 (b) Polyamide resin component forms a continuous phase,
(A) A model diagram of a phase structure in which a polyolefin resin component forms a dispersed phase.

FIG. 3 is a model diagram of a phase structure in which both (a) a polyolefin resin component and (b) a polyamide resin component form a continuous phase.

FIG. 4 is a front sectional view and a plan view of a barrier multilayer hollow container (after joining).

FIG. 5 is a front cross-sectional view and a plan view of a divided body (before joining) of a barrier multi-layer hollow container.

FIG. 6 is a front cross-sectional view and a plan view of a divided body (before joining) of a barrier multi-layer hollow container.

FIG. 7 is a test piece for evaluating the strength of a welded part cut out from a barrier multi-layer hollow container.

[Explanation of symbols]

1 Multi-layer hollow container 2 Multi-layer hollow container division 3 Multi-layer hollow container division 4 barrier layers 5 Thermoplastic resin layer 6 Welded part 7 openings 8 Test piece with welded part 9 Non-welded test piece

Front page continuation (51) Int.Cl. ⁷ identification code FI theme code (reference) B65D 65/40 B65D 77/06 H 4F206 77/06 C08K 7/00 4F213 C08K 7/00 C08L 23/00 4J002 C08L 23 / 00 77/00 77/00 B29K 23:00 // B29K 23:00 77:00 77:00 B29L 22:00 B29L 22:00 B65D 1/00 BCF term (reference) 3E033 AA06 BA13 BA14 BA21 BB04 BB08 CA09 DA06 DD01 FA02 GA02 3E061 AA30 AB12 AD04 AD09 DA01 DA12 DB06 3E067 AA03 AB96 BA01C BA11B BB14B BB14C BB25B BC07B BC07C CA04 CA24 EA06 FA04 FC01 3E086 BA04 BA15 BA35 BB51 BB74 CA29 4F100 AA03A AA03H AK01B AK03A AK06B AK46A AL05A AS00A BA02 BA10A BA10B BA15 DA01 EC032 EH361 EH362 GB16 GB32 JA11A JB16B JD02A JK01 JL02 4F206 AA03 AA29 AB11 AB16 AG07 AH55 AH56 JA05 JB22 JB28 JL02 CFW CL05 CLBBJBB05BBW BB21WBBW BB21WBBW BB21WJW21 4J002 BB21 4J002WBBW L05X CL08Y DJ006 DJ056 FA016 GF00 GG01

Claims (19)

[Claims] 1. A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin and (c) a liquid crystalline resin and / or (d) a layered silicate, and (e) a barrier layer. A multilayer hollow container having a thermoplastic resin layer made of a thermoplastic resin other than the resin composition to be formed, which has a welded part in a part of the hollow container, and the strength of the welded part is 50% or more of the non-welded part. A barrier multi-layer hollow container characterized by: 2. A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is perpendicular to the surface of the molded article. When the direction is taken as the thickness, a phase structure observed in an electron microscope in the resin molded product has (a) a polyolefin resin as a continuous phase and (b) a polyamide resin as a dispersed phase from the surface to the inner layer in the thickness direction. Part of
A barrier layer in which (b) the polyamide resin is the continuous phase and (a) the polyolefin resin is the dispersed phase, and (a) the polyolefin resin is the continuous phase and (b) the polyamide resin is the dispersed phase are sequentially observed. The barrier multi-layer hollow container according to claim 1, wherein 3. A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is perpendicular to the surface of the molded article. When the direction is taken as the thickness, (a) a continuous phase of the polyolefin resin and (b) a dispersed phase of the polyamide resin are observed at an arbitrary depth of 5 to 10% from the surface in the resin molded product. ,And,
The barrier layer in which (b) a continuous phase of the polyamide resin and (a) a dispersed phase of the polyolefin resin are observed at an arbitrary depth of 45 to 55% from the surface with respect to the total thickness. The multi-layer, hollow container having barrier properties described in 1. 4. A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is perpendicular to the surface of the molded article. As a phase structure observed by an electron microscope in the resin molded product, where (a) a polyolefin resin and (b) a polyamide resin are both continuous phases in the thickness direction from the surface to the inner layer. ,
It is a barrier layer in which (b) a part where the polyamide resin is a continuous phase and (a) a polyolefin resin is a dispersed phase, and (a) a part where the polyolefin resin and (b) a polyamide resin are both continuous phases are successively observed. Claim 1 characterized by
The multi-layer, hollow container having barrier properties described in 1. 5. A barrier layer formed of a resin composition comprising (a) a polyolefin resin, (b) a polyamide resin, (c) a liquid crystalline resin and / or (d) a layered silicate is perpendicular to the surface of the molded article. When the direction is taken as the thickness, (a) the polyolefin resin and (b) the polyamide resin are both observed as a continuous phase at an arbitrary depth of 5 to 10% from the surface in the resin molded product, and , At any depth from the surface to the total thickness of 45-55%, (b)
The barrier multi-layer hollow container according to claim 4, which is a barrier layer in which a continuous phase of a polyamide resin and a dispersed phase of (a) a polyolefin resin are observed. 6. When Tp (° C.) is the higher temperature of the melting points of the (a) polyolefin resin and (b) polyamide resin, the following formula (1) is obtained at an arbitrary temperature of Tp + 10 ° C. to Tp + 100 ° C. ), The melt viscosity ratio is 0.5 or less at an arbitrary shear rate of 200 sec ^-1 or less, and a shear rate of 1000 sec.
A barrier layer satisfying 0.8 or more at an arbitrary shear rate of ^-1 or more.
5. The barrier multi-layer hollow container according to any one of to 5. [Formula 1] 7. The barrier multilayer hollow container according to claim 1, wherein the thermoplastic resin other than the resin composition (e) forming the barrier layer is a polyolefin. 8. The barrier according to claim 1, which is welded by at least one method selected from injection welding, hot plate welding, vibration welding, heat ray welding and laser welding. Multi-layer hollow container. 9. The barrier multi-layer hollow container according to claim 1, wherein the barrier multi-layer hollow container has one or more openings formed of barrier layer components. 10. (a) Polyolefin resin, (b) Polyamide resin, (c) Liquid crystalline resin and / or (d)
A method for producing a multilayer hollow container having a barrier layer formed of a resin composition including a layered silicate and (e) a thermoplastic resin layer including a thermoplastic resin other than the resin composition forming the barrier layer, the method comprising: 2 constituting the multi-layer hollow container
One or more divided bodies are laminated by multicolor injection molding, and subsequently the obtained divided bodies are joined to each other to form a multilayer hollow container. The strength of the welded portion is 50% or more of that of the non-welded portion. A method for producing a multi-layer hollow container having barrier properties. 11. A (a) polyolefin resin, (b) polyamide resin, (c) liquid crystalline resin and / or (d).
When the thickness of the barrier layer formed by the resin composition composed of the layered silicate is perpendicular to the surface of the molded product, the phase structure observed in the resin molded product with an electron microscope shows a thickness direction from the surface to the inner layer. Toward (a) a portion where the polyolefin resin is a continuous phase and (b) a polyamide resin is a dispersed phase, (b) a portion where the polyamide resin is a continuous phase and (a) a polyolefin resin is a dispersed phase, (a) a polyolefin resin 11. The method for producing a barrier multi-layer hollow container according to claim 10, wherein a barrier layer in which the continuous phase and the portion where the polyamide resin is the dispersed phase (b) are sequentially observed is formed. 12. (a) Polyolefin resin, (b) Polyamide resin, (c) Liquid crystalline resin and / or (d)
When the thickness of the barrier layer formed of the resin composition composed of the layered silicate is perpendicular to the surface of the molded product, the thickness of the resin molded product is 5 to 10% of the total thickness from the surface of the molded product. , (A) a continuous phase of the polyolefin resin and (b) a dispersed phase of the polyamide resin are observed, and
A barrier layer in which (b) a continuous phase of a polyamide resin and (a) a dispersed phase of a polyolefin resin are observed at an arbitrary depth of 45 to 55% of the total thickness from the surface is formed. 11. The method for producing a barrier multi-layer hollow container according to item 11. 13. (a) Polyolefin resin, (b) Polyamide resin, (c) Liquid crystalline resin and / or (d)
When the thickness of the barrier layer formed by the resin composition composed of the layered silicate is perpendicular to the surface of the molded product, the phase structure observed in the resin molded product with an electron microscope shows a thickness direction from the surface to the inner layer. Toward (a) a portion where the polyolefin resin and (b) the polyamide resin are both continuous phases,
To form a barrier layer in which (b) a portion where the polyamide resin is a continuous phase and (a) a portion where the polyolefin resin is a dispersed phase, and (a) a portion where the polyolefin resin and (b) the polyamide resin are both a continuous phase are sequentially observed. The method for producing a barrier multi-layer hollow container according to claim 10. 14. (a) Polyolefin resin, (b) Polyamide resin, (c) Liquid crystalline resin and / or (d)
When the thickness of the barrier layer formed of the resin composition composed of the layered silicate is perpendicular to the surface of the molded product, the thickness of the resin molded product is 5 to 10% of the total thickness from the surface of the molded product. , (A) polyolefin resin and (b) polyamide resin are both observed as a continuous phase, and at an arbitrary depth from the surface of 45 to 55% of the total thickness,
The method for producing a barrier multi-layer hollow container according to claim 13, wherein a barrier layer in which a continuous phase of (b) a polyamide resin and a dispersed phase of (a) a polyolefin resin are observed is formed. 15. The following formula (1) at the temperature during molding process:
The melt viscosity ratio defined by is 0.5 or less at an arbitrary shear rate of 200 sec ^-1 or less, and
(A) a polyolefin resin, which has a shear rate of 0.8 or more at an arbitrary shear rate of 1000 sec- ¹ or more,
15. The barrier multi-layer hollow according to claim 10, wherein a resin composition comprising (b) polyamide resin, (c) liquid crystalline resin and / or (d) layered silicate is melt-molded. Container manufacturing method. [Formula 2] 16. (a) Polyolefin resin, (b) Polyamide resin, (c) Liquid crystalline resin and / or (d)
A barrier layer formed of a resin composition composed of a layered silicate and a thermoplastic resin layer formed of a thermoplastic resin other than the resin composition (e) forming the barrier layer (e) are laminated by two-color injection molding. The method for producing a barrier multi-layer hollow container according to any one of claims 10 to 15. 17. The divided bodies obtained by multicolor injection molding are joined to each other by at least one welding method selected from injection welding, hot plate welding, vibration welding, heat ray welding and laser welding. The method for producing a barrier multi-layer hollow container according to any one of claims 10 to 16. 18. The production of a barrier multi-layer hollow container according to claim 17, wherein the welding method for joining the divided bodies obtained by multicolor injection molding to each other is injection welding and / or vibration welding. Method. 19. The method for producing a barrier multi-layer hollow container according to claim 10, wherein one or more openings formed of barrier layer components are formed by multicolor injection molding. .