JP2001302910A - Resin molding for gas and/or liquid barrier component and chemical or gas transportation and/or storage container and its accessory made thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin molding for a gas and/or liquid barrier component exhibiting resistance to permeation of a gas and/or a liquid even when used at a high humidity and having excellent properties upon water absorption because it decreases little, for example, in dimensional change and mechanical properties such as rigidity upon moisture absorption. SOLUTION: Provided is a resin molding for a gas and/or liquid barrier component, comprising a resin composition substantially consisting of (a) a polyamide resin and (b) a polyolefin resin in a specified mixing ratio and, when observed with an electron microscope, having a specified resin phase separation structure such as one in which polyolefin resin (b) constitutes a matrix phase (continuous phase), and polyamide resin (a) constitutes a disperse phase.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a structure having excellent resistance to gas and / or liquid permeation.
In particular, to gas and / or liquid barrier parts having specific permeation resistance, low water absorption, dimensional stability when absorbing moisture, and moldability, which are obtained by forming a specific phase structure between polyamide resin and polyolefin resin. The present invention relates to a resin molded body suitable for application of the present invention.

[0002]

2. Description of the Related Art Polyamide resins are widely used for electric / electronic parts, automobile parts, etc. because of their well-balanced mechanical properties, heat resistance, chemical resistance and moldability. In recent years, resin molded products that require gas barrier properties for the purpose of preventing leakage of contents and preventing intrusion of outside air in order to ensure safety, storage stability, and environmental pollution prevention properties have been increasing. Among them, polyamide resins have been used as various molded articles because of their excellent gas barrier properties. However, polyamide resins have higher toughness due to moisture absorption, but have reduced dimensional changes and rigidity, and furthermore, have low permeation resistance to chemicals and gases when used under high humidity, thus restricting the range of use. It is often the case that this is done, and improvement is desired.

[0003] In order to supplement the physical properties of such polyamide resins, resin compositions and molded articles combining a polyolefin resin having problems in rigidity, gas barrier properties, heat resistance, etc., while having excellent water resistance and molding workability, are provided. Have been proposed in the past.

However, these methods certainly improve the dimensional stability and rigidity at the time of water absorption as compared with a single polyamide resin, but are not always satisfactory. In addition, it is not sufficient when used for members that require permeation resistance and rigidity, and a resin molded article having both a characteristic possessed by these polyamide resins and a characteristic possessed by a polyolefin resin and having an excellent property balance is provided. There is a further need.

[0005]

An object of the present invention is to realize a high balance between the mechanical strength and permeation resistance of a polyamide resin and the low water absorption and toughness of a polyolefin resin. Suitable for application to resin moldings, especially gas and / or liquid barrier parts, where the reduction of mechanical properties such as dimensional change and rigidity due to moisture absorption, which are the essential characteristics, and the reduction of the permeation resistance of chemicals and gases are suppressed as much as possible. It is an object of the present invention to provide a polyamide-polyolefin-based resin molded article for a gas and / or liquid barrier component.

[0006]

The inventors of the present invention have studied to solve the above-mentioned problems, and as a result, a specific amount of a polyamide resin and a polyolefin resin are blended, and if necessary, an inorganic filler is blended. The present inventors have found that the above-mentioned problems can be solved by controlling the dispersed structure of the molded article so that the polyolefin resin phase forms a continuous phase in the molded article, and the present invention has achieved the present invention.

[0007] That is, the above-mentioned object is achieved by (1) a resin composition consisting essentially of (a) 5 to 80% by volume of a polyamide resin and (b) 95 to 20% by volume of a polyolefin resin, and observed by an electron microscope. And (b) forming a phase structure in which the polyolefin resin forms a matrix phase (continuous phase), and (a) the polyamide resin forms a dispersed phase.
Or a resin molding for a liquid barrier component. (2) a resin composition comprising (a) 15 to 85% by volume of a polyamide resin and (b) 85 to 15% by volume of a polyolefin resin, and (b) a polyolefin having a resin phase separation structure observed by an electron microscope A resin molded article for gas and / or liquid barrier parts, characterized in that the resin phase and the polyamide resin phase (a) together form a substantially continuous phase structure. (3) (a) 5 to 80% by volume of a polyamide resin and (b)
In a resin phase separation structure observed by an electron microscope, (b) a continuous phase composed of a polyolefin resin and (a) a strip-shaped dispersed phase composed of a polyamide resin are constituted by a resin composition comprising 95 to 20% by volume of a polyolefin resin. A resin molded article for a gas and / or liquid barrier component, characterized by forming a phase structure comprising: (4) A container for transporting and / or storing a chemical solution or gas obtained by processing them, and an accessory thereof.
Is achieved by

[0008]

Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”. The polyamide resin (a) used in the present invention is a polyamide containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the components include 6-aminocaproic acid and 11-aminocaproic acid.
Aminoundecanoic acid, 12-aminododecanoic acid, amino acids such as paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, Decamethylenediamine, dodecamethylenediamine, 2,2,4
-/ 2,4,4-trimethylhexamethylenediamine,
5-methylnonamethylenediamine, meta-xylylenediamine, para-xylylenediamine, 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-
Aliphatic, alicyclic and aromatic diamines such as aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, spearic acid and azelaine Acid, sebacic acid, dodecanedioic acid,
Such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid Examples thereof include aliphatic, alicyclic and aromatic dicarboxylic acids. In the present invention, nylon homopolymers or copolymers derived from these components can be used alone or in the form of a mixture.

In the present invention, a polyamide resin having a melting point of 150 ° C. or more is excellent in heat resistance and strength and can be particularly preferably used. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene Dodecamide (nylon 612), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene Terephthalamide copolymer (nylon 66 / 6T), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66 copolymer), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 6/6
I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T
/ 6I), polyhexamethylene terephthalamide / polydodecaneamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), poly Hexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I
/ 6), polyxylylene adipamide (nylon XD
6), polyhexamethylene terephthalamide / poly-2
-Methylpentamethylene terephthalamide copolymer (nylon 6T / M5T) and mixtures thereof.

Particularly preferred polyamide resins include nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T
/ 12, and copolymers having hexamethylerephthalamide units such as nylon 6T / 6 copolymer. These polyamide resins may be further used in accordance with required properties such as impact resistance, molding processability, and compatibility. Use as a mixture is also practically suitable.

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 5.
Polyamide resins in the range of 0, especially in the range of 2.0 to 4.0 are preferred.

The polyolefin resin 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 homopolymers such as polyethylene, polypropylene and copolymerized polypropylene containing polypropylene as a main component, polystyrene, polyacrylate, polymethacrylate, poly 1-butene, poly 1-pentene, polymethylpentene, and the like. Ethylene / α-olefin copolymer, vinyl alcohol ester homopolymer, polyolefin resin obtained by hydrolyzing at least a part of vinyl alcohol ester homopolymer, [(ethylene and / or propylene) and vinyl alcohol ester Polyolefin resin obtained by hydrolyzing at least a part of [copolymer], [copolymer of ((ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [( Ethylene and / or propylene And (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)
And a block copolymer of a conjugated diene and a vinyl aromatic hydrocarbon, and a hydride thereof. Among these polyolefin resins, it is particularly preferable to use polyethylene, polypropylene, copolymerized polypropylene mainly composed of polypropylene, and ethylene / α-olefin copolymer. It is practically preferable to use two or more kinds of polyolefin resins in combination according to the need for post-processability such as bonding with other resins.

The above polypropylene is not particularly limited, and any of isotactic, atactic, syndiotactic and the like can be used. In addition to the homopolymer, a block with another olefin component containing 70% by weight or more of a propylene component or a random copolymer can be used.

The polyolefin resin of the present invention preferably has a melt flow rate (MFR) of 0.01 to 70 g / 10 min, more preferably 0.03 to 60 g / min.
10 minutes. When the MFR is less than 0.01 g / 10 min, the fluidity is poor, and when it exceeds 70 g / 10 min, the impact strength is lowered, which is not preferable. The MFR may be prepared by thermally decomposing a polymerized polyolefin resin together with an organic peroxide.

The method for producing the polyolefin resin (b) used in the present invention is not particularly limited, and may be any of radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, and coordination polymerization using a metallocene catalyst. Can also be used.

In the present invention, the polyolefin resin is preferably used after being modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides and derivatives thereof. By using the modified modified polyolefin, compatibility can be further improved, and a molded article having extremely excellent impact resistance while maintaining moldability can be obtained. Unsaturated carboxylic acid used as a modifier, examples of compounds selected from acid anhydrides or derivatives thereof include acrylic acid, methacrylic acid, maleic acid,
Fumaric acid, itaconic acid, crotonic acid, methyl maleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, Butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride , Itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-
2,3-dicarboxylic acid, endobicyclo- (2,2,
1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate,
Glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid.
Of these, unsaturated dicarboxylic acids and their anhydrides are preferred, especially maleic acid, 5-norbornene-
2,3-dicarboxylic acids or their anhydrides are preferred.

The method for introducing a compound selected from these unsaturated carboxylic acids, anhydrides or derivatives thereof into the polyolefin resin is not particularly limited, and the olefin compound as the main component and the unsaturated carboxylic acid, the acid Methods such as copolymerizing a compound selected from an anhydride or a derivative thereof, and graft-introducing a compound selected from an unsaturated carboxylic acid, an acid anhydride or a derivative thereof to a non-modified polyolefin resin using a radical initiator. Can be used. The amount of the modifier component to be introduced is preferably from 0.001 to 40 mol%, more preferably from 0.01 to 40 mol%, based on the entire olefin monomer in the modified polyolefin.
Suitably, it is in the range of 35 mol%.

The inorganic filler (c) used in the present invention is not particularly limited, but fibrous, plate-like, powder-like, and granular fillers can be used. Specifically, glass fiber, PAN-based or pitch-based carbon fiber,
Metal fibers such as stainless steel fiber, aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool Fibrous, whisker-like filler such as potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica,
Examples of the filler include powdery, granular, and plate-like fillers such as calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wallastenite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Among them, glass fibers and PAN-based carbon fibers are preferably used when conductivity is required. The type of the glass fiber is not particularly limited as long as it is generally used for reinforcing a resin. For example, a long fiber type or a short fiber type chopped strand, a milled fiber or the like can be used. The above fillers can be used in combination of two or more kinds. The filler used in the present invention can be used after its surface is treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, or the like) or another surface treatment agent. The glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

The amount of addition of the above-mentioned inorganic filler is 1 in total of the polyamide resin (a) and the polyolefin resin (b).
The amount is preferably 5 to 200 parts by weight based on 00 parts by weight. More preferably, it is 5 to 150 parts by weight, particularly preferably 5 to 100 parts by weight. 20 inorganic fillers added
If the amount is more than 0 parts by weight, the moldability and appearance are deteriorated, which is not preferable.

In the resin molded article for gas and / or liquid barrier parts of the present invention, the mixing ratio of the polyamide resin (a) and the polyolefin resin (b) is such that the polyolefin resin component forms a continuous phase (matrix phase). When the polyamide resin component has a phase structure in which a dispersed phase is formed (for example, a sea-island structure), the polyamide resin 5 to 8
0% by volume and 95 to 20% by volume of polyolefin resin. Preferably, the content is 55 to 80% by volume of the polyamide resin and 45 to 20% by volume of the polyolefin resin. When such a polyolefin resin component is a small component, a phase structure in which the polyolefin resin takes a continuous phase can be formed, for example, by appropriately controlling the melt viscosity ratio of the polyamide resin / polyolefin resin. A molded article having this phase structure is particularly preferable because it has an excellent balance between the properties at the time of water absorption and the resistance to permeation. Furthermore, the mixing ratio of both components is 60 to 75% by volume of the polyamide resin,
It is preferably 0 to 25% by volume. When the amount of the polyamide resin (a) exceeds 80% by volume, it becomes difficult for the polyolefin resin component, which is a feature of the resin molded article of the present invention, to form a continuous phase, and the object of the present invention cannot be achieved. Further, when the content of the polyamide resin (a) is less than 5% by volume, the permeation resistance of the resin molded product is lowered, which is not preferable.

Next, when obtaining a molded product having a phase structure (for example, a sea-sea structure) in which the polyolefin resin component and the polyamide resin component together form a substantially continuous phase (matrix phase), 15 to 85% by volume of the polyamide resin is used. In the composition range of 85 to 15% by volume of the polyolefin resin, it is important to control the melt viscosity and the compatibility of the polyamide resin and the polyolefin resin. To realize this phase separation structure, a composition of 30 to 70% by volume of a polyamide resin and 70 to 30% by volume of a polyolefin resin is preferable, and 35 to 65% by volume of a polyamide resin and 65 to 65% of a polyolefin resin.
35% by volume is more preferred. When the polyamide resin of the component (a) exceeds 85% by volume or less than 15% by volume, it becomes difficult for the polyolefin resin component to form a substantially continuous phase, and a molded article that can achieve the object of the present invention is obtained. I can't get it.

Next, when the polyolefin resin component forms a continuous phase (matrix phase) and the polyamide resin component forms a strip-shaped dispersed phase (laminar structure), the polyamide resin 5-80% by volume, the polyolefin resin 95-95% 2
0% by volume. Preferably a polyamide resin 25 to 70
% By volume, 75 to 30% by volume of a polyolefin resin, more preferably 55 to 70% by volume of a polyamide resin, and 45 to 30% by volume of a polyolefin resin. When the amount of the polyamide resin (a) exceeds 80% by volume, it becomes difficult for the polyolefin resin component to form a continuous phase, and the object of the present invention cannot be achieved. On the other hand, if the amount of the polyamide resin (a) is less than 5% by volume, it is difficult to obtain a sufficient length and amount of the band-shaped dispersed phase of the polyamide resin component, and the object of the present invention cannot be achieved.

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

Specific examples of the layered silicate include various clay minerals such as smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite, vermiculite, halloysite, kanemite, keniyaite, zirconium phosphate, titanium phosphate and the like. And swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, etc., and may be natural or synthesized. . Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable synthetic mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferred.

The layered silicate used in the present invention is preferably a layered silicate in which the exchangeable cation existing between the layers is an organic onium ion.

Examples of the organic onium ion include an ammonium ion, a phosphonium ion, and a sulfonium ion. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferably used. As ammonium ions,
Primary ammonium ion, secondary ammonium ion, 3
Any of a quaternary ammonium ion and a quaternary ammonium ion may be used.

The primary ammonium ion includes decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Examples of the secondary ammonium ion include methyl dodecyl ammonium, methyl octadecyl ammonium, and the like. Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium. As quaternary ammonium ions, benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium,
Benzyltrialkylammonium ions such as benzyldimethyloctadecyl ammonium, trioctylmethylammonium, trimethyloctylammonium,
Examples include alkyltrimethylammonium ions such as trimethyldodecylammonium and trimethyloctadecylammonium, and dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium.

In addition, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-Ammonium ions derived from aminododecanoic acid and the like.

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

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

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined in consideration of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, and the suppression of generation of odor. Typically 0.4 for cation exchange capacity
It is preferably in the range of 2.0 to 2.0 equivalents, more preferably 0.8 to 1.2 equivalents. In addition, these layered silicates may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, in addition to the above-mentioned organic onium salt. good.

Preferred coupling agents include organic silane compounds. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-
Ureido group-containing alkoxysilane compounds such as (2-ureidoethyl) aminopropyltrimethoxysilane;
-Isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as ethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ Amino-containing alkoxysilane compounds such as -aminopropyltrimethoxysilane, and hydroxyl-containing alkoxysilanes such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Alkoxysilanes containing carbon-carbon unsaturated groups such as run compounds, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride And the like. Particularly, an alkoxysilane compound having a carbon-carbon unsaturated group is preferably used.

The treatment of the phyllosilicate with these coupling agents can be carried out in a polar solvent such as water, methanol or ethanol.
Alternatively, a method of adsorbing the coupling agent to the layered silicate in these mixed solvents or a method of dropping and adsorbing the coupling agent solution while stirring the layered silicate in a high-speed stirring mixer such as a Henschel mixer, Further, any method may be used, in which a silane coupling agent is directly added to the layered silicate and mixed and adsorbed in a mortar or the like. When treating a layered silicate with a coupling agent,
It is preferable to simultaneously mix water, acidic water, alkaline water and the like in order to promote the hydrolysis of the alkoxy group of the coupling agent. Further, in order to enhance the reaction efficiency of the coupling agent, water such as methanol or ethanol and an organic solvent which dissolves both the coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the layered silicate treated with such a coupling agent. Note that a so-called integral blending method of adding these coupling agents when melt-kneading the layered silicate and the polyamide resin without previously treating the layered silicate with the coupling agent may be used.

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. However, it is preferable to first treat the layered silicate with the organic onium ion and then treat with the coupling agent.

In the present invention, the content of the layered silicate (d) is defined as an inorganic ash content, and is 0.1 to 50 parts by weight based on 100 parts by weight of the total of (a) the polyamide resin and (b) the polyolefin resin. And more preferably 1 to 20 parts by weight, particularly preferably 1.5 to 10 parts by weight. If the content is too small, the effect of improving physical properties is small, and if the content is too large, the toughness may decrease. The amount of the inorganic ash can be determined by ashing 2 g of the resin composition in an electric furnace at 500 ° C. for 3 hours.

A conductive filler and / or a conductive polymer can be used for imparting conductivity to the resin composition for gas and / or liquid barrier parts of the present invention, and is not particularly limited. However, as the conductive filler, there is no particular limitation as long as it is a conductive filler that is usually used for making a resin conductive. Specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, metal oxide, and conductive powder. Examples include inorganic filler, carbon powder, graphite, carbon fiber, carbon flake, and flaky carbon coated with a substance.

Specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal type of the metal fiber include iron, copper, stainless steel, aluminum, and brass. Such metal powder, metal flakes, metal ribbons, and metal fibers may be subjected to a surface treatment with a surface treatment agent such as a titanate, aluminum, or silane.

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

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

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black and the like according to its raw material and production method. The raw material and the production method of the carbon powder that can be used in the present invention are not particularly limited, but acetylene black and furnace black are particularly preferably used. Various carbon powders having different properties such as particle diameter, surface area, DBP oil absorption, and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in these properties, but from the viewpoint of strength and electrical conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm,
Further, the thickness is preferably 10 to 70 nm. The surface area (BET
Law) is 10 m ² / g or more, more preferably at least 30 m ² / g. The DBP lubrication amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. The ash content is 0.
It is preferably at most 5%, particularly preferably at most 0.3%.

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

A molded article obtained by processing the resin composition for a gas and / or liquid barrier component of the present invention often requires a smooth surface. From such a viewpoint, the conductive filler used in the present invention is more powdery, granular, plate-like, scale-like, or fibrous filler having a high aspect ratio, like the inorganic filler (c) used in the present invention. It is preferable that the resin composition is in any fibrous form having a length / diameter ratio of 200 or less.

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

The above-mentioned conductive filler and / or conductive polymer may be used in combination of two or more kinds. Among these conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and economy.

Although the content of the conductive filler and / or the conductive polymer used in the present invention varies depending on the type of the conductive filler and / or the conductive polymer used, it cannot be specified unconditionally. (A) and (b) in terms of balance with the mechanical strength, etc.
1 to 25 based on 100 parts by weight of the total of the component and the component (c)
A range of 0 parts by weight, preferably 3 to 100 parts by weight, is preferably selected.

When conductivity is imparted, its volume resistivity is 10 ¹⁰ Ω · c in order to obtain sufficient antistatic performance.
m or less. However, the blending of the above-mentioned conductive filler and conductive polymer generally tends to cause deterioration in strength and fluidity. Therefore, if a target conductivity level is obtained, it is desirable that the amount of the conductive filler and the conductive polymer is as small as possible. The target conductivity level depends on the application, but usually the volume resistivity is 100Ω
cm and not more than 10 ¹⁰ Ω · cm.

In the polyamide resin of the present invention, a copper compound can be preferably used in order to improve long-term heat resistance. Specific examples of copper compounds include 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 inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Among them, monovalent copper compounds, particularly monovalent copper halide compounds, are preferred, and cuprous acetate, cuprous iodide and the like can be exemplified as particularly suitable copper compounds. The amount of the copper compound to be added is usually preferably 0.01 to 2 parts by weight, more preferably 0.015 to 1 part by weight, based on 100 parts by weight of the polyamide resin. If the addition amount is too large, metal copper is released during melt molding, and the value of the product is reduced by coloring. In the present invention, it is also possible to add an alkali halide in a form used in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide, and potassium iodide, iodine Sodium chloride is particularly preferred.

In the composition of the present invention, other components such as an antioxidant and a heat stabilizer (a hindered phenol type, a hydroquinone type, a phosphite type and substituted products thereof) are provided as long as the effects of the present invention are not impaired. ), Weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various bisamides) , Bisurea, 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 (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), difficult Flame retardants (for example, hydroxides such as red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc., ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin and brominated epoxy resins thereof) Combination of flame retardant and antimony trioxide),
Other polymers can be added.

The method of adjusting the dispersion state is not particularly limited as long as a resin molded product satisfying the requirements specified in the present invention can be obtained. In this melt-kneading, a preferable dispersion state is achieved by, for example, twin screw extrusion. When melt kneading with an extruder, the polyamide resin and polyolefin resin are supplied from the main feeder, and the inorganic filler is supplied from the side feeder at the tip of the extruder. A method of melting and kneading with a filler is exemplified. In addition, when the layered silicate is blended with the polyamide resin and the polyolefin resin, either a method in which the layered silicate is present in the polymerization system of the polyamide resin or a method in which both are melt-kneaded may be used.

The method for molding the resin molded article for gas and / or liquid barrier parts of the present invention is not limited, and any known method (injection molding, extrusion molding, blow molding, press molding, etc.) can be used. Preferred methods include injection molding, injection compression molding, and compression molding. Also,
The molding temperature is usually 10 points below the melting point of the polyamide.
It is selected from a temperature range higher by ５０50 ° C. and is generally a single layer, but may be a multilayer by a two-color molding method.

The arrangement of each layer in the resin molded article of the present invention is not particularly limited, and all the layers may be constituted by the resin molded article for gas and / or liquid barrier parts of the present invention, or may be formed in other layers. It may be constituted by using other thermoplastic resin or a resin molded product for gas and / or liquid barrier component without filler. The layer composed of the resin molded article for gas and / or liquid barrier parts of the present invention is preferably the innermost layer in the case of two layers in order to sufficiently exhibit the permeation resistance effect.

The thermoplastic resin used as a layer other than the resin molded product for a gas and / or liquid barrier component of the present invention used herein includes saturated polyester, polysulfone, polyethylene tetrafluoride, polyetherimide,
Polyamide-imide, polyamide, polyketone copolymer,
Polyphenylene ether, polyimide, polyether sulfone, polyether ketone, polythioether ketone, polyether ether ketone, thermoplastic polyurethane, polyolefin, ABS, polyamide elastomer,
Polyester elastomer can be exemplified, and if necessary,
One or more of these thermoplastic resins may be used in combination, or various additives may be added thereto to impart desired physical properties. Further, the obtained molded articles may be bonded or welded to each other or to another molded article. The method is not particularly limited, and a general technique can be used.

The resin molded article for gas and / or liquid barrier parts of the present invention is, for example, Freon-11 or Freon-1.
2, Freon-21, Freon-22, Freon-113, Freon-114, Freon-115, Freon-134a, Freon-32, Freon-123, Freon-124, Freon-125, Freon-143a, Freon-141b, Freon-142b, Freon-225, Freon-C318, R
-502, 1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform,
Propane, isobutane, n-butane, dimethyl ether, castor oil-based brake fluid, glycol ether-based brake fluid, borate ester-based brake fluid, brake fluid for extreme cold regions, silicone oil-based brake fluid, mineral oil-based brake fluid, power slurry oil , Window washer liquid, gasoline, methanol, ethanol, isoptanol, butanol, nitrogen, oxygen, hydrogen, carbon dioxide, methane, propane, natural gas, argon, helium, xenon, gas and / or liquid or vaporized gas such as pharmaceutical agents Because of its low permeability even when absorbing water, it can be used for chemical storage containers such as fuel tanks, oil reservoir tanks, and other types of chemical bottles such as shampoo, rinse and liquid soap, or cuts attached to these tanks and bottles. A valve such as an off valve Bed and fittings, gauge accessory pump, parts such as case include, fuel filler under the pipe, ORVR hose, a reserve hose, various fuel tube connection parts such as the vent hose (connectors, etc.),
Oil tube connection parts, brake hose connection parts, nozzles for window washer fluid, cooling water, refrigerant hose connection parts, refrigerant air conditioner refrigerant tube connection parts, fire extinguishers and fire extinguishing equipment hoses, medical cooling equipment tubes Connection parts and valves, other chemical liquid and gas transfer tube applications, chemical storage containers and other chemical liquid and gas permeation resistant applications, automotive parts,
Including internal combustion engine applications, mechanical parts such as power tool housings, electrical and electronic parts, medical care, food, home and office supplies,
It is effective for various uses such as building material related parts and furniture parts.

[0054]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the gist of the present invention is not limited to the following Examples. (1) Alcohol gasoline permeability A die for forming a tube at the tip of an extruder having a diameter of 40 mm, a sizing die for cooling and controlling the size of the tube,
A tube having an outer diameter of 8 mm and an inner diameter of 6 mm was formed using a take-up machine. The tube is 20c
The tube was cut to a length of m, one end of the tube was sealed, and 6 g of an alcohol gasoline mixture obtained by mixing a commercial regular gasoline and ethanol in a 75:25 weight ratio was weighed and charged inside, and the other end was also sealed. Thereafter, the entire weight was measured, and the test tube was placed in an explosion-proof oven at 40 ° C., treated for 500 hours, and the reduced weight was measured. (2) Permeability of alcohol gasoline when absorbing moisture A test tube filled with an alcohol gasoline mixture in the same manner as in (1) above was treated for 500 hours in a thermo-hygrostat at a temperature of 40 ° C. and a relative humidity of 65%, and the reduced weight was measured. It was measured. (3) Oxygen permeability GTR- according to JIS K7126 A method (differential pressure method)
10 (manufactured by Yanako Kagaku Kogyo). (4) Material strength Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod Impact strength: ASTM D256 (5) Water absorption Using an ASTM No. 1 test piece (1/8 inch thick) at a constant temperature and humidity of 60 ° C. and 95% relative humidity. The sample was allowed to stand in a vessel for 24 hours, and the weight increase upon water absorption was determined from the weight at the time of absolute drying immediately after molding (at the time of absolute drying) and the weight after water absorption. Water absorption (%) = {(weight after water absorption-weight when absolutely dry) / weight when absolutely dry} x 100 (6) Dimensional stability at the time of water absorption Immediately after the absolute drying (absolute drying) and the length of the test piece after water absorption (longitudinal direction), it was determined as a dimensional increase rate upon water absorption. Dimensional stability at the time of water absorption (%) = {(test piece length after water absorption-test piece length at absolute dryness) / test piece length at absolute dryness} x 100 (7) Elastic modulus at water absorption Same as the above water absorption rate The flexural modulus of the test piece subjected to the water absorption treatment was measured. (8) Observation of phase separation structure The cross-section of the tube molded product
Observation was performed using M). (9) Melt viscosity ratio Using a plunger-type capillary rheometer, a melt viscosity (p) at a shear rate of 10 sec ^-1 at the melt-kneading temperature.
oise) was measured and determined. Melt viscosity ratio = melt viscosity of polyamide resin ÷ melt viscosity of polyolefin resin The polyamide resins and polyolefins used in Examples and Comparative Examples are as follows. Reference Example 1 Na-type montmorillonite (Kunimine Industries: Knipia F,
100 g of a cation exchange capacity (120 meq / 100 g) was stirred and dispersed in 10 liters of warm water, and 2 L of warm water in which 48 g (equivalent to the cation exchange capacity) of trioctylmethylammonium chloride was dissolved, and stirred for 1 hour. . The resulting precipitate was separated by filtration and washed with warm water. This washing and filtration were repeated three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organic layered silicate. When the amount of inorganic ash in this organically modified layered silicate was measured, the proportion of inorganic ash was 67% by weight. The inorganic ash content is a value obtained by incinulating 0.1 g of layered silicate in an electric furnace at 500 ° C. for 3 hours. <Polyamide resin> (N6-1): Nylon 6 resin having a melting point of 225 ° C and a relative viscosity of 2.80. (N6-2): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 3.30. (N6-3): Nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 4.30. (N6-4): 100 parts by weight of a nylon 6 resin having a melting point of 225 ° C. and a relative viscosity of 2.80 was mixed with 5 parts of the organically modified layered silicate obtained in Reference Example, and
Layered silicate-containing nylon 6 resin obtained by melt extrusion at a cylinder temperature of 250 ° C. using a screw extruder. (N66): Nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of 3.20. (N6 / 66): Nylon 6/66 copolymer having a melting point of 217 ° C. and a relative viscosity of 2.85. <Polyolefin resin> (PP-1): polypropylene (MFR = 10) 100
Parts by weight, 0.8 parts of maleic anhydride, 2,5-dimethyl-
Modified polypropylene obtained by mixing 0.05 parts of 2,5-di (tert-butylperoxy) hexane and melt-extruding the mixture at a cylinder temperature of 220 ° C. using a twin-screw extruder. (PP-2): polypropylene (MFR = 0.5) 10
0 parts by weight, 0.8 parts of maleic anhydride and 0.05 parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane were mixed, and the cylinder temperature was 220 ° C. using a twin-screw extruder. Modified polypropylene obtained by melt extrusion. (PP-3): polypropylene (MFR = 10). (PE-1): 100 parts by weight of polyethylene (MFR = 30), 1 part of maleic anhydride, 2,5-dimethyl-2,5
0.1 part of di (tert-butylperoxy) hexane was mixed, and the cylinder temperature was 220 ° C. using a twin-screw extruder.
Modified polyethylene obtained by melt extrusion. (PE-2): low-density polyethylene (ethylene / hexene copolymer, MFR = 4) produced by a metallocene-based catalyst having a density of 0.905. Examples 1 to 14 and Comparative Examples 1 to 6 As shown in Tables 1 and 2, a polyamide resin and a polyolefin resin were mixed and supplied from a main feeder of a TEX30 type twin screw extruder manufactured by Nippon Steel Works, and an inorganic filler was supplied. In this case, melt-kneading was performed at a kneading temperature of 250 ° C. (280 ° C. for N66) and a screw rotation speed of 200 rpm by a method of supplying using a side feeder in the middle of the cylinder. After drying the obtained pellets, injection molding (Toshiba Machine IS100F
A, a mold temperature was 80 ° C) to prepare a test piece. Table 1 shows the results of measurement of the permeation resistance, material strength, and properties during water absorption of each sample. 1 (Example 7) and FIG. 2 (Comparative Example 6) show electron micrographs for evaluating the phase separation structure. Here, GF in the table is glass fiber (fiber diameter 10 μm, 3 mm chopped strand, manufactured by NEC Corporation), and MF is milled fiber (average fiber length 140 μm, average fiber diameter 9 μm,
(Manufactured by NEC Corporation).

[0055]

[Table 1]

[0056]

[Table 2] The resin molded product of the present invention in which a specific phase separation structure is defined from Examples 1 to 14 and Comparative Examples 1 to 6 has good permeation resistance, and particularly, permeation resistance when absorbing water, dimensional stability, and when absorbing water. It is of high practical value with excellent rigidity characteristics.

[0057]

The resin molded product of the present invention has good gas and / or liquid barrier properties, and particularly has good permeation resistance and rigidity even under high humidity, so that it can be developed for various uses. Suitable for electrical / electronic related equipment, precision machine related equipment, office equipment, automobile / vehicle related parts, building materials, packaging materials, furniture, household goods, etc.

[Brief description of the drawings]

FIG. 1 is an electron micrograph showing a phase separation structure of Example 7, in which a portion dyed black is a polyamide resin component.

FIG. 2 is an electron micrograph showing the phase separation structure of Comparative Example 6, in which a portion stained black is a polyamide resin component.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int. Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/00 C08L 23/00 23/04 23/04 23/10 23/10 23/26 23/26 77 / 02 77/02 77/06 77/06 // (C08L 77/00 (C08L 77/00 23:00) 23:00) F term (reference) 3E086 AA21 AD04 BA02 BA15 BA35 BB01 BB41 BB71 BB74 CA28 CA29 4F071 AA20 AA54 AA55 AA78 AA88 AB28 AD01 AE17 AF08 AF09 AH05 BA01 BB03 BB05 BB06 BC01 BC04 4J002 BB03X BB05X BB12X BB15X BB17X BB21X BB23X BC03X BE02X BF02X BF03X BG04X BG05X BG103 BP01X CL01W CL02W CL03W CL05W CL063 DA026 DA076 DA096 DA116 DB006 DE106 DE136 DE146 DE186 DE236 DG026 DG056 DH056 DJ006 DJ007 DJ016 DJ026 DJ036 DJ046 DJ056 DK006 DL006 DM006 FA016 FA017 FA043 FA046 FA066 FA086 FD016

Claims (15)

[Claims] (1) Substantially (a) 5-80 polyamide resin
% And (b) 95 to 20% by volume of polyolefin resin
And a phase structure in which (b) the polyolefin resin is a matrix phase (continuous phase) and (a) the polyamide resin is a dispersed phase in a resin phase separation structure observed by an electron microscope. A resin molded article for a gas and / or liquid barrier component, characterized in that: 2. The gas and / or liquid according to claim 1, wherein the mixing ratio of (a) the polyamide resin and (b) the polyolefin resin is 55 to 80% by volume and 45 to 20% by volume, respectively. Resin molding for barrier parts. 3. The gas and / or liquid according to claim 1, wherein the mixing ratio of (a) the polyamide resin and (b) the polyolefin resin is 60 to 75% by volume and 40 to 25% by volume, respectively. Resin molding for barrier parts. 4. (a) 15 to 85% by volume of a polyamide resin
And (b) a resin composition composed of 85 to 15% by volume of a polyolefin resin, and (b) a phase composed of a polyolefin resin and (a) a phase composed of a polyamide resin in a resin phase separation structure observed by an electron microscope. Have a phase structure that is a substantially continuous phase. 5. A resin phase-separated structure composed of (a) a resin composition comprising 5 to 80% by volume of a polyamide resin and (b) 95 to 20% by volume of a polyolefin resin, and having a resin phase separation structure observed by an electron microscope. A) A resin molded article for a gas and / or liquid barrier component, which forms a phase structure composed of a continuous phase composed of a polyolefin resin and a band-shaped dispersed phase composed of (a) a polyamide resin. 6. The gas and / or liquid according to claim 5, wherein the mixing ratio of (a) the polyamide resin and (b) the polyolefin resin is 25 to 70% by volume and 75 to 30% by volume, respectively. Resin molding for barrier parts. 7. The composition according to claim 1, further comprising (d) 0.1 to 50 parts by weight of a layered silicate based on 100 parts by weight of the total of the polyamide resin (a) and the polyolefin resin (b). Item 7. A resin molded article for a gas and / or liquid barrier component according to any one of Items 1 to 6. 8. The composition according to claim 1, further comprising 5 to 200 parts by weight of an inorganic filler (c) based on 100 parts by weight of the total of the polyamide resin (a) and the polyolefin resin (b). 7. The resin molded article for a gas and / or liquid barrier component according to any one of 6. 9. The resin molded article for gas and / or liquid barrier parts according to claim 1, wherein the polyolefin resin as the component (b) contains polyethylene or polypropylene. 10. The polyolefin resin (b) contains a modified polyolefin resin modified by at least one compound selected from unsaturated carboxylic acids, acid anhydrides and derivatives thereof. 10. The resin molded article for a gas and / or liquid barrier component according to any one of 1 to 9. 11. The resin molded article for gas and / or liquid barrier parts according to claim 10, wherein the polyolefin resin as the component (b) contains a polypropylene modified with an unsaturated carboxylic anhydride. 12. The method according to claim 1, wherein the polyamide resin as the component (a) comprises a nylon 6 resin as a main component.
The resin molded article for a gas and / or liquid barrier component according to any one of claims 1 to 7. 13. The method according to claim 1, wherein the polyamide resin as the component (a) has a nylon 66 resin as a main component.
12. The resin molded article for a gas and / or liquid barrier component according to any one of 11. 14. The resin for gas and / or liquid barrier parts according to claim 1, wherein a method for obtaining a molded body is selected from injection molding, injection compression molding, and compression molding. Molded body. 15. A chemical or gas carrier and / or storage container obtained by processing the resin molded article for a gas and / or liquid barrier component according to claim 1, and an accessory part thereof.