JP2001172445A - Resin composition having resistance to gas and/or liquid permeability and its molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having resistance to gas and/or liquid permeability, enabling improvement in surface appearance, processing stability, vibration-damping property and dimensional stability in use in water absorption as well as improvement in resistance to gas and/or liquid permeability, and a molded product thereof. SOLUTION: This resin composition having resistance to gas and/or liquid permeability comprises (A) 50-99.9 wt.% saponified product of an ethylene-vinyl acetate copolymer having 20-60 mol% ethylene content and >=90 mol% saponification degree of vinyl acetate component and (B) 50-0.1 wt.% liquid crystalline resin. In the resin composition, the component B is dispersed into a matrix of the component A, and >=60 wt.% disperse particles of the component B has 0.5 α to 1.5 α disperse particle diameter (α is weight average disperse particle diameter).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas and / or liquid permeation resistance, vibration damping property, dimensional stability upon absorption of water, suppression of gelation due to stagnation, and thickness of a molded article. The present invention relates to a gas and / or liquid permeation-resistant resin composition having improved moldability such as improvement of unevenness, and a molded article thereof.

[0002]

2. Description of the Related Art In recent years, resin molded articles requiring gas barrier properties have been increasing, and among them, ethylene-vinyl acetate copolymer (EVOH) has excellent oxygen gas permeability, mechanical properties, Because of its excellent balance of properties such as abrasion resistance and chemical resistance, it is used as various molded products. However, since the polymer has a hydroxyl group in the main chain, the water absorption is large, and the oxygen gas transmission resistance and water vapor transmission resistance during water absorption are not sufficient. In addition, when molding, particularly when molding large-sized molded articles, or when used for blow molding or extrusion molding of film tubes, etc., gelation due to stagnation occurs and continuous good molded articles cannot be obtained. There is a problem that the use is restricted.

[0003]

SUMMARY OF THE INVENTION Accordingly, the present invention solves the above-mentioned problems, including improving the permeation resistance of gas and / or liquid, damping properties, dimensional change upon absorption of water, and forming process. It is an object of the present invention to obtain a gas- and / or liquid-permeation-resistant resin composition which suppresses gelation of a molded article, improves the thickness unevenness of the molded article at the time of blowing or extrusion molding, and obtains the molded article.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the following conclusions and have reached the present invention.

That is, the present invention relates to (1) a saponified ethylene-vinyl acetate copolymer (A) having an ethylene content of 20 to 60 mol% and a saponification degree of a vinyl acetate component of 80 mol% or more (A) 50 to 99.9% by weight. % And liquid crystalline resin (B) 5
A resin composition (C) comprising 0 to 0.1% by weight;
Are dispersed in the matrix of (A), and (B)
A gas and / or liquid permeation-resistant resin composition, wherein 60% by weight or more of the dispersed particles have a dispersed particle size of 0.5α to 1.5α (α is a weight average dispersed particle size);
(2) The weight average dispersed particle diameter of the liquid crystalline resin (B) is 0.0
A gas- and / or liquid-resistant resin composition according to the above (1), wherein the resin composition (C) is any one of the above (1) or (2). A gas and / or liquid permeation-resistant resin composition obtained by adding 0.5 to 200 parts by weight of a filler to 100 parts by weight, and (4) ethylene-acetic acid at a temperature equal to or lower than the melting point of the liquid crystal resin (B). The saponified vinyl copolymer (A) and the liquid crystalline resin (B) are melt-kneaded to obtain the above (1) to
(3) A method for producing a gas and / or liquid permeation-resistant resin composition, which comprises producing the gas and / or liquid permeation-resistant resin composition according to any one of (1) to (5). 3) A gas- and / or liquid-permeation-resistant hollow molded article comprising the gas- and / or liquid-permeation-resistant resin composition according to any one of (6) and (6) wherein the hollow molded article according to (5) is a gas- and / or liquid- (7) The gas- and / or liquid-resistant resin composition according to any one of the above (1) to (3), which is used for a transport line / storage container or an accessory thereof. A transfer line / storage container obtained by injection molding or an accessory thereof, (8) a gas and / or liquid comprising the gas and / or liquid-resistant resin composition according to any one of the above (1) to (3). Or liquid There is provided a permeable film.

[0006]

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

[0007] The saponified ethylene-vinyl acetate copolymer (EVOH) used in the present invention is:
It is obtained by copolymerizing and saponifying ethylene and vinyl acetate. The ethylene content is 20 to 60 mol%, and the saponification degree of the vinyl acetate component is 80% or more. The ethylene content is preferably from 25 to 55 mol%, more preferably from 30 to 40 mol%. The degree of saponification of the vinyl acetate component is preferably at least 85%, more preferably at least 90%. If the ethylene content is too low, the molding temperature will approach the decomposition temperature, and molding tends to be difficult. On the other hand, if the ethylene content is too large, the gas barrier properties tend to decrease. In addition, the degree of saponification of the vinyl acetate component is too small, and EVOH is apt to cause gelled substances,
In addition, gas barrier properties tend to be low.

[0008] The melt viscosity of EVOH is not particularly limited. However, when determined as a melt flow rate (MFR), the melt viscosity of EVOH may be 210 points from the viewpoints of moldability, dispersibility during blending, and the like.
° C, the value measured under a load of 2160 g is preferably 0.1 to
50 g / 10 min, more preferably 0.3 to 20 g / 10
Minutes are used.

[0009] The EVOH used in the present invention may have units derived from other copolymerizable monomers. Examples of such monomers include polyfunctional (e.g., triallyl cyanurate, triallyl isocyanurate, diallyl maleate, diallyl fumarate, diallyl phthalate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol diacrylate, and the like). (Meth) acrylic compounds and the like. The polyfunctional monomer can be copolymerized into the EVOH in any form, such as conventional copolymerization or graft polymerization. When a polyfunctional monomer is copolymerized, the ratio is 0.002.
It is preferable to keep it at about 0.2 mol%.

The liquid crystalline resin (B) of the present invention is a polymer capable of forming an anisotropic molten phase upon melting, and includes liquid crystalline polyester, liquid crystalline polyester amide, liquid crystalline polycarbonate, liquid crystalline polyester elastomer and the like. Among them, those having an ester bond in the molecular chain are preferable, and liquid crystal polyester and liquid crystal polyesteramide are particularly preferably used.

The liquid crystalline resin (B) which can be preferably used in the present invention is a liquid crystalline polyester containing a structural unit composed of p-hydroxybenzoic acid as an aromatic oxycarbonyl unit, and an ethylenedioxy unit as an essential component. Liquid crystalline polyester can also be preferably used. More preferred are polyesters consisting of the following structural units (I), (III) and (IV) or polyesters consisting of the structural units of (I), (II), (III) and (IV), the most preferred being ( I),
It is a polyester comprising the structural units of (II), (III) and (IV).

[0012]

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(Where R ₁ in the formula is

[0014]

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R ₂ represents one or more groups selected from

[0016]

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And represents one or more groups selected from Also,
In the formula, X represents a hydrogen atom or a chlorine atom. Note that the sum of structural units (II) and (III) and structural unit (IV)
Are desirably substantially equimolar.

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-butylhydroquinone, phenylhydroquinone, methylhydroquinone, 2,6-dihydroxynaphthalene, 2,7- Dihydroxynaphthalene,
Structural units formed from one or more aromatic dihydroxy compounds selected from 2,2-bis (4-hydroxyphenyl) propane and 4,4'-dihydroxydiphenyl ether, and structural unit (III) is a structure formed from ethylene glycol. Structural unit (IV) is terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid,
6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,4'- Each of one or more structural units generated from an aromatic dicarboxylic acid selected from diphenyl ether dicarboxylic acids is shown. Of these, R ₁ is

[0019]

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And R ₂ is

[0021]

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Are particularly preferred.

The above structural units (I), (II), (III) and (IV)
Is arbitrary. However, in order to exhibit the characteristics of the present invention, the following copolymerization amount is preferable.

That is, the structural units (I), (II) and (II)
I), in the case of a copolymer consisting of (IV), the structural unit (I)
The total of (II) and (II) is preferably from 30 to 95 mol%, more preferably from 40 to 93 mol%, based on the total of the structural units (I), (II) and (III). The structural unit (III) is the structural unit
It is preferably from 70 to 5 mol%, more preferably from 60 to 7 mol%, based on the total of (I), (II) and (III). The molar ratio of the structural unit (I) to (II) [(I) / (II)] is preferably from 75/25 to 95/5, and more preferably from 78/25.
22 to 93/7. The structural unit (IV) is the structural unit
It is preferably substantially equimolar to the sum of (II) and (III).

On the other hand, when the above-mentioned structural unit (II) is not contained, from the viewpoint of fluidity, the structural unit (I) should be 40 to 90 mol% based on the total of the structural units (I) and (III). Is preferably 60 to 88 mol%, and the structural unit (IV) is preferably substantially equimolar to the structural unit (III).

Here, "substantially equimolar" means that the units constituting the polymer main chain excluding the terminal are equimolar, but the units constituting the terminal are not necessarily equimolar.

Further, as the liquid crystalline polyesteramide,
Polyesteramides that form an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) are preferred.

The liquid crystalline polyesters and liquid crystalline polyesteramides which can be preferably used include, in addition to the components constituting the structural units (I) to (IV), 3,3'-diphenyldicarboxylic acid and 2,2 ' -Aromatic dicarboxylic acids such as diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4′- Dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxybenzophenone, 3,4 '
-Aromatic diols such as dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, and aliphatic and fats such as 1,4-cyclohexanedimethanol Cyclic diols, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, and p-aminobenzoic acid can be further copolymerized to the extent that liquid crystallinity is not impaired.

The method for producing the liquid crystalline resin (B) 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) p-acetoxybenzoic acid and diacylated aromatic dihydroxy compounds such as 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 polycondensation reaction therefrom. (2) Reaction of aromatic dihydroxy compounds such as p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl and hydroquinone with aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid, and acetic anhydride. The phenolic hydroxyl group is acylated, and then a liquid crystalline polyester is produced by a deacetic acid polycondensation reaction. (3) Phenyl esters of p-hydroxybenzoic acid and aromatic dihydroxy compounds such as 4,4'-dihydroxybiphenyl and hydroquinone and diphenyl esters of aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid For producing liquid crystalline polyesters from polyphenols by a dephenol removal polycondensation reaction. (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, terephthalic acid, or isophthalic acid to form diphenyl esters, respectively.
A method in which an aromatic dihydroxy compound such as 4,4'-dihydroxybiphenyl or hydroquinone is added, and a liquid crystalline polyester is produced by a phenol-elimination polycondensation reaction. (5) In the presence of a bis (β-hydroxyethyl) ester of an aromatic dicarboxylic acid such as a polymer or oligomer of a polyester such as polyethylene terephthalate or an aromatic dicarboxylic acid such as bis (β-hydroxyethyl) terephthalate, the liquid crystal is prepared by the method of (1) or (2). A method for producing a conductive polyester.

The melt viscosity of the liquid crystalline resin (B) is not particularly limited, but in order to further exhibit the effects of the present invention,
The value measured at the melting point of the liquid crystalline resin + 10 ° C. is 100 Pa ·
s or less, more preferably 0.1 to
It is 50 Pa · s, most preferably 0.5 to 30 Pa · s. Here, the melt viscosity is determined at a shear rate of 1,000.
(1 / sec) Nozzle diameter 0.5mmφ, nozzle length 10mm
Are values measured by a Koka type flow tester using the nozzle of No.

Here, the melting point is defined as Tm1 + 20 ° C. after the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured from room temperature under a heating condition of 20 ° C./min. After holding at the temperature of 5 minutes, 2
Once cooled to room temperature at 0 ° C./min,
The melting point is the endothermic peak temperature (Tm2) observed when the measurement is performed under the temperature rising condition of 0 ° C./min.

The compounding ratio of the EVOH (A) and the liquid crystalline resin (B) used in the present invention is excellent in gas and / or liquid permeation resistance, vibration damping, dimensional stability when absorbing water, and gelation during processing. (A) 99.9 to 50% by weight with respect to the sum of (A) and (B) from the viewpoints of suppression and molding workability such as wall thickness uniformity.
(B) 0.1 to 50% by weight, preferably (A) 95 to 7
0% by weight, (B) 5 to 30% by weight, more preferably (A) 92 to 80% by weight, and (B) 8 to 20% by weight.

The composition of the present invention usually has a structure in which the liquid crystalline resin (B) is dispersed in the matrix resin EVOH (A). The present invention has the effects of the present invention in which the dispersion diameter distribution of the liquid crystalline resin (B) dispersed in the EVOH (A) is the effect of the present invention, such as gas and / or liquid permeation resistance, vibration damping properties, and dimensional stability when absorbing water. In order to exhibit the effect of (1), it is essential that 60% or more of the dispersed particles of the liquid crystalline resin have a dispersed particle diameter of 0.5α to 1.5α (α is a weight average dispersed diameter), preferably 70 % Or more, more preferably 75% or more is within the above range.

The weight-average dispersion diameter is not particularly limited.
In order to further exhibit effects such as gas and / or liquid permeation resistance, vibration damping properties, and dimensional stability when absorbing water, the thickness is preferably 0.01 to 5 μm, more preferably 0.02 to 5 μm. 3 μm, more preferably 0.05 to 2 μm
m.

In order to further improve the gas and / or liquid permeation resistance and vibration damping effect of the present invention, there is no particular limitation.
Among the dispersed particles of the liquid crystalline resin (B) dispersed in the VOH (A), the aspect ratio represented by the major axis / minor axis of the particles is 3
The above is preferably 10% or more, more preferably 2% or more.
0% or more.

A method for measuring the weight average dispersion diameter of the liquid crystalline resin (B) in the EVOH (A) is as follows. Observation and photography were performed using a scanning microscope (TEM), and the average value of 100 dispersed particles was determined as the weight average dispersion diameter. The dispersed particle diameter is measured in the major axis direction, and the aspect ratio is determined by measuring the major axis direction / minor axis direction, respectively, and determining the ratio.

A filler can be used to impart mechanical strength and other properties to the gas and / or liquid permeation resistant resin composition of the present invention. A filler such as a plate, a powder, and a granule can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless steel fiber,
Metal fiber such as aluminum fiber and brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber,
Fibrous, whisker-like fillers such as silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, mica, talc, kaolin, silica, carbonic acid Examples of the filler include powdery, granular, and plate-like fillers such as calcium, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, walastenite, titanium oxide, zinc oxide, calcium polyphosphate, and graphite. Among the above fillers, 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. Further, two or more of the above fillers can be used in combination. The filler used in the present invention may 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 covered 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 the filler added is EVOH (A)
And 100 parts by weight of the total amount of the liquid crystalline resin (B),
It is 0.5 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.

The filler used in the present invention is EVO
After the melt-kneading of H and the liquid crystalline resin, the ratio of the filler having a long diameter or a fiber length of 60 μm or less is controlled in the range of 5 to 50% by weight in the total filler, particularly in a state of being subjected to one melt-kneading. Is preferred. This is because the presence of a specific amount of a filler having a major axis or a fiber length of 60 μm or less can provide a molded article of the resin composition having particularly good surface appearance.

A particularly desirable ratio of the filler having a major axis or a fiber length of 60 μm or less is in the range of 10 to 40% by weight.
If the proportion of the filler having a particle size of 60 μm or less is too small, the surface appearance is slightly lower than the preferable conditions, and if it is too large, there is a concern that the mechanical strength may be adversely affected.

The average thickness (short diameter) or average fiber diameter of the filler in the composition is not particularly limited.
μm is preferred.

Particularly when glass fibers are used as the filler, a particularly favorable effect is exhibited by making the distribution state in the composition as described above. Alternatively, a bulk filler can be used in combination.

The reinforced resin composition having such a major diameter distribution or fiber length distribution is preferably obtained in a single melt-kneading step from the viewpoint of production efficiency. As an example of an efficient method for realizing this, a strand length of 1 mm or more is used. A method in which a filler such as glass fiber and glass fiber having a fiber length of 20 to 500 μm or mica having an average particle size distribution of 5 to 200 μm is used as a mixture in an appropriate ratio as a raw material can be mentioned.

As the combination, the average fiber diameter is 5 to 15 μm,
Glass fiber with a strand length of 1 mm or more and an average fiber diameter of 5
A mixture with a filler such as glass fiber having a strand length of 20 to 500 μm is preferably used. When two or more types of glass fibers having different strand lengths are used in combination, it is also a preferable method to use glass fibers having different average diameters of 2 μm or more.

The method for measuring the thickness (short diameter) or the fiber diameter and the long diameter or the fiber length of the filler in the composition is as follows: about 5 g of the composition is ashed in a crucible, and 100 mg of the remaining filler is ashed. Collect and disperse in 100 cc of soapy water. Then, one to two drops of the dispersion are placed on a slide glass using a dropper, observed under a microscope, and photographed. Measure the length and thickness of the filler taken in the photograph or the fiber length and fiber diameter. When determining the fiber length of the carbon fiber, care must be taken because if the ashing conditions are incorrect, the fiber itself may be oxidized and burned, and it is desirable to incinerate in a nitrogen atmosphere. When the thermoplastic resin to be used is soluble, the composition can be dissolved using a solvent, the fiber can be taken out, and the fiber length can be measured. The measurement is performed for 300 or more pieces, and the ratio of 60 μm or less is calculated.

It is possible to use a conductive filler and / or a conductive polymer for imparting conductivity to the gas and / or liquid permeation resistant resin composition of the present invention,
Although it is not particularly limited, 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, and metal fiber. , A metal oxide, an inorganic filler coated with a conductive substance, carbon powder, graphite, carbon fiber, carbon flake, and flaky carbon.

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

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

The metal powder, metal flake, metal ribbon, and metal fiber may be subjected to a surface treatment with a surface treating 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),
Examples thereof include ZnO (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),
Examples include n ₂ O ₃ (antimony doping). 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 preferably 0.5% or less, particularly preferably 0.3% or less.

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 gas and / or liquid permeation resistant resin composition of the present invention often requires a smooth surface. From such a viewpoint, the conductive filler used in the present invention, like the filler used in the present invention, is more powdery, granular, plate-like, flaky, or resin composition than a fibrous filler having a high aspect ratio. It is preferable that the medium has any fibrous form having a length / diameter ratio of 200 or less.

Specific examples of the conductive polymer used in the present invention 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 such conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and cost.

The conductive filler used in the present invention and / or
Alternatively, since the content of the conductive polymer varies depending on the type of the conductive filler and / or the conductive polymer used, it cannot be unconditionally specified, but from the viewpoint of a balance between conductivity, fluidity, mechanical strength, and the like, the following is required. The following range is preferable.
That is, in the case of the conductive polymer, a range of 1 to 250 parts by weight, preferably 3 to 100 parts by weight is preferably selected with respect to 100 parts by weight of the total of the components (A) and (B). Since the conductive filler is a kind of the filler, the amount of the conductive filler is considered as the number of filler components.

When conductivity is imparted, the volume specific resistance 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 can be obtained, it is desirable that the amount of the conductive filler and conductive polymer is as small as possible. The target conductivity level depends on the application, but usually the volume resistivity is usually
The range is more than ¹⁰⁰ Ω · cm and 10 ¹⁰ Ω · cm or less.

In order to further impart properties such as improved impact strength to the gas and / or liquid permeation resistant resin composition of the present invention, an olefin compound having a carboxylic acid anhydride group in the molecule or these olefins, if necessary, Compound polymers may be blended, and specific examples include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, aconitic anhydride, and polymers of these substituted olefin compounds. In the olefin compound polymer, olefins other than the olefin compound having a carboxylic anhydride group in the molecule, such as styrene, isobutylene, methacrylic acid ester, and acrylic acid ester, are copolymerized within a range that does not impair the effects of the present invention. Although it does not matter, it is preferable that the polymer is substantially composed of a polymer of an olefin compound having a carboxylic anhydride group in the molecule. The polymerization degree of the olefin compound polymer is 2 to 10.
0 is preferable, 2 to 50 is more preferable, and 2 to 2 is more preferable.
0 is most preferred. Among them, maleic anhydride and polymaleic anhydride are most preferably used. Examples of polymaleic anhydride include, for example, J. Macromol. Sci.-Revs.
Macromol. Chem., C13 (2), 235 (1975) and the like can be used.

The olefin compound having a carboxylic anhydride group in the molecule or the polymer of the olefin compound is added in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Part is preferable from the viewpoint of the effect of improving the impact strength and the fluidity of the composition, and more preferably 0.1 to
It is preferably in the range of 5 parts by weight, more preferably 0.1 to 3 parts by weight.

The olefin compound having a carboxylic anhydride group in the molecule or a polymer of these olefin compounds used herein may have an anhydride structure when substantially melt-kneaded with the polyamide resin. The compound or the polymer of the olefin compound is hydrolyzed and subjected to melt-kneading in the form of a carboxylic acid or an aqueous solution thereof. It may be kneaded.

For example, when it is necessary to further improve the permeation resistance of a gas and / or liquid permeation-resistant resin composition such as a chemical and a gas, an acid anhydride or a polyepoxy compound can be added. is there. Examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride,
Examples include acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, trimellitic anhydride, 1,8-naphthalic anhydride, phthalic anhydride, and maleic anhydride, among which succinic anhydride, 1,8-naphthalic anhydride, and anhydrous Phthalic acid, maleic anhydride and the like are preferably used. The polyvalent epoxy compound is a compound having two or more epoxy groups in a molecule. Preferably, the polyepoxy compound is selected from polyfunctional epoxy compounds having an epoxy equivalent of 100 to 1000. Examples of such a polyvalent epoxy compound include a novolak type epoxy compound obtained by reacting a novolak resin (phenol novolak, cresol novolak, etc.) with epichlorohydrin. Or
Compounds obtained by reacting a compound having two or more active hydrogens in one molecule with epichlorohydrin or 2-methylepichlorohydrin are exemplified. Examples of the compound having two or more active hydrogens in one molecule include polyhydric phenols (bisphenol A, bishydroxydiphenylmethane, resorcin, bishydroxydiphenyl ether, tetrabromobisphenol A, etc.), polyhydric alcohols (ethylene glycol, Pentyl glycol,
Glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, bisphenol A-ethylene oxide adduct, trishydroxyethyl isocyanurate, etc., amino compounds (eg, ethylenediamine, aniline, etc.), polyvalent carboxy compounds (eg, adipic acid, phthalic acid) , Isophthalic acid, etc.). Examples of such polyepoxy compounds include terephthalic acid diglycidyl ester, triglycidyl cyanurate, hydroquinone diglycidyl ether, N, N'-diglycidylaniline, and the like. Other examples include linear aliphatic epoxy compounds such as butadiene dimer epoxide and epoxidized soybean oil, and alicyclic epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene diepoxide. These may be used alone or in combination of two or more.

The amount of the acid anhydride or polyepoxy compound used in the present invention depends on EV resistance from the viewpoint of improving permeation resistance.
The amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight, per 100 parts by weight of OH (A). By using the acid anhydride, the dispersion particle size distribution width of the liquid crystal resin dispersed in the EVOH (A) is narrowed, and as a result, the addition of the liquid crystal resin exerts a more excellent improvement in transmission resistance. However, when the amount of the acid anhydride or the polyhydric epoxy compound is too large, gas is generated at the time of melt-kneading and molding, and poor biting, gas burning of the molded product and rupture and tearing of the molded product at the time of blowing or extrusion molding and gas are generated. Gelation occurs due to the cause of leakage or excessive reaction, and in the worst case, molding becomes impossible. Further, for example, even if a molded product is obtained, the obtained molded product also tends to have reduced mechanical properties as well as surface appearance.

The state of the acid anhydride or polyepoxy compound used in the present invention in the gas and / or liquid permeation resistant resin composition is not particularly limited.
Water or EVOH, liquid crystalline resin and its monomer
It may be present in any state of a reaction product with the oligomer.

The gas and / or liquid permeation resistant resin composition of the present invention contains at least one selected from the group consisting of alkoxysilanes, preferably epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups and ureido groups. Addition of alkoxysilane having a functional group has mechanical strength,
It is effective in improving toughness and the like. Specific examples of such compounds include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
epoxy group-containing alkoxysilane compounds such as β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Mercapto group-containing alkoxysilane compounds such as mercaptopropyltriethoxysilane; ureide group-containing such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compound, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane;
Amino-containing alkoxysilane compounds such as -aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ- Hydroxy group-containing alkoxysilane compounds such as hydroxypropyltriethoxysilane and the like.

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) may be used as long as the effects of the present invention are not impaired. ), Weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), 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 Combustion agents (for example, hydroxides such as red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, etc., ammonium polyphosphate, brominated polystyrene, brominated PPO, brominated PC, brominated epoxy resin, or brominated epoxy resins thereof) Other polymers, such as a combination of a flame retardant and antimony trioxide).

The method for producing the composition of the present invention is not limited as long as a resin composition satisfying the conditions specified in the present invention can be obtained. However, it is preferable to exhibit the characteristics of the present invention most efficiently in melt-kneading. In order to realize the dispersion state of the liquid crystalline resin, the melting and kneading temperature is preferably not higher than the melting point of the liquid crystal resin to be used, more preferably not higher than -5 ° C, more preferably not higher than -10 ° C. The lower limit of the melt processing temperature is not limited as long as it can be melt-kneaded, and is equal to or higher than the melting point of EVOH.

The melting and kneading apparatus is not particularly limited, and a known apparatus can be used, for example, a single-shaft, twin-shaft, kneader or the like. Further, since it is preferable to be as stiff as possible, it is preferable to use a device in which several kneading disks are inserted with a twin-screw extruder,
Knead.

When other fillers and additives are added, they may be added at any stage in the preferred kneading method with the EVOH (A) and the liquid crystalline resin (B). Specifically, after melt-kneading EVOH and other additives such as acid anhydride or polyepoxy compound, elastomer and the like, a liquid crystal resin, a method of kneading with a filler,
A method in which all components are kneaded together, a method in which EVOH and an acid anhydride or a polyvalent epoxy compound, and a liquid crystalline resin are kneaded and then a filler and other additives are kneaded, and a method in which EVOH and an acid anhydride or a polyvalent are once kneaded. After kneading an epoxy compound and a liquid crystalline resin into a resin composition (Z), a high-concentration composition (master) (M) of a filler is prepared using the obtained resin composition (Z). Either method may be used.

The method for molding the gas- and / or liquid-permeable resin composition of the present invention is not limited, and any known method (such as injection molding, extrusion molding, blow molding, press molding) can be used. As a method for obtaining an item that requires the effects of the present invention, general methods include extrusion molding, blow molding, press molding, and the like. However, if injection molding such as accessory parts is possible, it is most preferable in terms of production.

For example, although not particularly limited, the molding temperature is usually in a temperature range of 10 to 100 higher than the melting point of EVOH, preferably in a temperature range of 15 to 80 ° C. higher than the melting point.
Particularly preferably, it is selected from the temperature range of 20 to 70 ° C. higher than the melting point and the melting point of the liquid crystalline resin or lower.
Although it is a single layer, it may be a multilayer.

In the case of injection molding, the resin composition is usually made of one kind of the resin composition of the present invention, but two-color molding or the like may be used for the purpose of forming a multilayer.

In the case of blow molding, after a parison is formed using a usual blow molding machine, blow molding may be performed at an appropriate temperature. In addition, the form of blow molding is also a single-layer molded body,
Any of multilayer molded bodies may be used. Extrusion molding (for tubes,
The same applies to blow molding, and a die having the shape obtained at the tip of the extruder is attached to obtain a single-layer molded product or a multilayer molded product.

Next, a multi-layer molded product which is an example of the method for producing a molded product of the present invention will be described by way of example, but is not limited to the following. That is, the molten resin extruded from the extruder of the number of layers or the number of materials is introduced into one multi-layer die, and bonded in the die or immediately after leaving the die to produce a multilayer molded body. Can be. Alternatively, a method may be used in which a single-layer molded body is once manufactured, and another layer is laminated on the inside or outside thereof to produce a multilayer molded body.

In the case of producing a multilayer molded article having a multilayer structure of three or more layers, extruders are appropriately added, each extruder is connected to a co-extrusion die, and a multilayer parison is extruded. It can be obtained by:

The arrangement of each layer in the multilayer molded article of the present invention is not particularly limited, and all the layers may be composed of the gas and / or liquid permeation-resistant resin composition of the present invention. The gas and / or liquid permeation-resistant resin composition of the present invention may be used, and another layer may be formed using another thermoplastic resin. The layer composed of the gas and / or liquid permeation-resistant resin composition of the present invention sufficiently exhibits its gas permeation resistance effect. In the case of two layers, the innermost layer, in the case of three or more layers, the innermost layer or It is preferably an intermediate layer.

The thermoplastic resin used herein other than the thermoplastic resin composition of the present invention includes saturated polyester resin, polysulfone resin, polyethylene tetrafluoride resin, polyetherimide resin, polyamideimide resin, polyamide resin, polyphenylene ether. Resins, polyimide resins, polyethersulfone resins, polyetherketone resins, polythioetherketone resins, polyetheretherketone resins, thermoplastic polyurethane resins, polypropylene, polyethylene and other polyolefin resins, cyclic olefins and other novel olefin resins, ABS resin, polyamide elastomer, polyester elastomer, and the like can be exemplified. If necessary, one or more of these thermoplastic resins may be blended and used, or various additives may be added to them to obtain desired products. It is of course also possible to use the grant.

The obtained molded products may be bonded or welded to each other or to other molded products. The method is not particularly limited, and a general technique (vibration welding, heat welding, laser welding, etc.) may be used. Is possible.

The molded article obtained from the gas- and / or liquid-permeable resin composition of the present invention is, for example, Freon-1
1, Freon-12, Freon-21, Freon-22, Freon-113, Freon-114, Freon-115, Freon-134a, Freon-32, Freon-123, Freon-
124, Freon-125, Freon-143a, Freon-
141b, Freon-142b, Freon-225, Freon-C318, R-502, 1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil base Brake fluid, glycol ether brake fluid, borate ester brake fluid, brake fluid for extreme cold, silicone oil brake fluid,
Mineral oil-based brake fluid, power drilling oil, window washer fluid, gasoline, methanol, ethanol,
Low permeability and low vibration of gas and / or liquid (and vaporized gas) such as isoptanol, butanol, hydrogen, nitrogen, oxygen, carbon dioxide, methane, propane, argon, helium, xenon, pharmaceutical agents, etc. Properties, such as excellent dimensional stability at the time of water absorption, for example, including the above-mentioned gas and / or liquid permeation-resistant film, an air bag, a chemical liquid storage tank, a gas storage tank, a cooling liquid tank, Automobile parts such as oil transfer tank, disinfectant tank, transfusion pump tank, fuel tank, fuel tank member, washer liquid tank, washer liquid tank member, oil reservoir tank, oil reservoir tank member, etc., parts for medical equipment, And shampoo, rinse, liquid Bottles for various chemicals such as soaps and detergents, and chemical storage containers such as auxiliary pumps or their accessories, brake hoses and their components, nozzles for window washer fluid, tubes for air conditioner refrigerant and their connecting components, floor heating pipes, fuel tubes And its components, fire extinguishers and hoses for fire extinguishing equipment, tubes for medical cooling equipment and components and valves for connecting them, other chemical and gas transport tube applications, and chemical and gas permeation resistance such as containers for storing chemicals are required. Applications, automotive parts, internal combustion engine applications, mechanical parts such as power tool housings, electrical and electronic parts such as calculators, acoustic parts, fan parts, etc., vacuum insulation boards such as refrigerators and cold storage, medical care, food ,
Household and office supplies, building materials-related parts such as wallpaper, furniture parts,
In addition, it is effective for various uses such as gas bags, balloons, and airships.

[0082]

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.

Reference Example 1 (Saponified ethylene-vinyl acetate copolymer) "EVAL" EP-F 101 (manufactured by Kuraray Co., Ltd.) Ethylene content 32 mol%, saponification degree 99.5% Reference Example 2 (liquid crystalline resin) B-1) 901 parts by weight of p-hydroxybenzoic acid, 4,4
126 parts by weight of '-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 of acetic anhydride
A weight part was charged into a reaction vessel equipped with a stirring blade and a distilling tube, and as a result of polymerization, aromatic oxycarbonyl unit was 72.5 parts.
265 ° C, 275 ° C melt viscosity 13 Pa · s (orifice 0.5 mmφ) consisting of molar equivalents, 7.5 molar equivalents of aromatic dioxy units, 20 molar equivalents of ethylenedioxy units, and 27.5 molar equivalents of aromatic dicarboxylic acid units. × 10mm,
A liquid crystalline resin having a shear rate of 1,000 (1 / sec) was obtained.

Examples 1 and 2, Comparative Examples 1 to 3 PCM30 type twin screw extruder (manufactured by Ikegai Iron & Steel Co., Ltd.) at the compounding ratios shown in Table 1, and (a) three kneading blocks at two locations ( Using a screw set in front of the vent and the tip portion, or a screw in which three (2) kneading blocks were set in front of the vent, saponified ethylene-vinyl acetate copolymer (A-1, manufactured by Kuraray Co., Ltd.) EVAL "EP-F101, melting point 181 ° C, MFR 1.3
g / 10 minutes (190 ° C., 2160 g)) and the liquid crystalline resin (B-1) were charged from a resin raw material feeder and melt-kneaded at a cylinder temperature of 230 ° C. The resulting composition was pelletized, vacuum dried at 80 ° C. for 10 hours, and evaluated by the following method. (1) Moisture permeability A T-die was attached to the tip of an extruder having a diameter of 40 mm, and a film having a thickness of about 30 µm was formed at a cylinder temperature of 230 ° C. Then, the obtained film was cut into 60 mmφ, and GTR-10 (produced by Yanaco Analytical Industry Co., Ltd.) according to
Was measured under the conditions of 40 ° C. and 90% RH. (2) Gelling properties (processability and surface appearance) The product was supplied to a Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) and the cylinder temperature was 230.
℃, mold temperature 80 ℃, 70mm × 70mm × 1mm thick square-formed product was molded in 15 shots at a cycle of 2 minutes / shot, and the molded product obtained at the 20th shot was processed at the processing temperature shown in Table 1. A pressed sheet having a thickness of 100 μm was prepared, and the presence or absence of unmelted material was examined.

The evaluation was ○: no unmelted material, ×: unmelted material. (3) Dimensional stability It was supplied to Sumitomo Nestor injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.) and the cylinder temperature was 230.
℃, the mold temperature is set to 80 ℃, the molded product (100mm × 1
(2.7mm × 1mm thickness), 35 ℃ / 95% RH
Was performed for 100 hours under the conditions described above, and the dimensional change rate was calculated by the following equation. [(Length in the flow direction of the moisture-absorbed product) / (length in the flow direction of the absolutely dry product)] × 100 (%) (4) Uniformity of wall thickness 230 Using a blow molding machine having an extruder having a diameter of 40 mm.
A bottle-shaped molded product having an outer diameter of 50 mm, a length of 200 mm, and a thickness of 2 mm was formed at a temperature of 40 ° C., and the thickness of the molded product was measured at 40 mm from the upper and lower ends and at the midpoint (100 mm from the top). (5) Vibration Suppression (Number of Amplitudes) Provided to Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature 230
℃, the mold temperature is set to 80 ℃, the molded product (100mm × 1
2.7mm x 3.2mm thickness) amplitude pre-amplifier (B & K type 2639S) and power amplifier (B & K type 2706) and 2-channel FFT analyzer (B & K
2034). ) Was performed in the range of 200 to 300 Hz. (6) Dispersion Diameter and Distribution of Liquid Crystalline Resin Observation and photographing of a section obtained by cutting the center of a 3.2 mm thick bending test piece prepared in accordance with ASTM D790 in the flow direction with an electron transmission microscope (TEM). Then, the average value of 100 dispersed particles was determined as a weight average dispersion diameter. The dispersed particle diameter was measured in the major axis direction. The dispersion diameter distribution was calculated from the dispersion diameters of the dispersed particles determined above.

Example 3, Comparative Examples 4 and 5 Using a TEX30 type twin screw extruder (manufactured by Nippon Steel Works Ltd.), EVOH and a liquid crystalline resin (B-
1) was charged from the resin raw material feeder, the filler shown in Table 2 was charged from the side feeder, and the cylinder temperature was 23.
The mixture was melt-kneaded at 0 ° C. The resulting composition was pelletized, vacuum dried at 80 ° C. for 10 hours, and evaluated by the following method. (7) Molded product warpage Provided to Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), cylinder temperature 230
℃, mold temperature 80 ℃, box-shaped molded product (external dimensions 30 mm × 30 mm × 10 mm (height) ×
1mm thick) and box-shaped products (outside dimensions 29mm x 29mm x 2)
(0 mm (height) x 1 mm), and the fitting was evaluated. In the evaluation, ○: fit, ×: sled and not fit.

[0087]

[Table 1]

As is evident from the results in Table 1, the gas and / or liquid permeation-resistant resin composition of the present invention was processed to obtain gas and / or liquid compared with the conventional saponified ethylene-vinyl acetate copolymer. Alternatively, it is possible to obtain a molded product having low liquid permeability as well as good moldability, vibration damping properties, and dimensional stability when absorbing water. From the results shown in Table 2, it is reinforced with a filler. Thereby, when used in injection molding, a material having low warpage can be obtained.

[0089]

The resin composition of the present invention has good resistance to gas and / or liquid permeation, and the resulting molded article has good surface appearance, vibration damping properties, and dimensional stability when absorbing water. Therefore, it can be applied to various uses, and is suitable for, for example, electric / electronic-related equipment, precision machinery-related equipment, office equipment, automobile / vehicle-related parts, building materials, packaging materials, furniture, and daily necessities.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission Date] July 13, 2000 (2007.1)
3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Change

[Correction contents]

The molded article obtained from the gas- and / or liquid-permeable resin composition of the present invention is, for example, Freon-1
1, Freon-12, Freon-21, Freon-22, Freon-113, Freon-114, Freon-115, Freon-134a, Freon-32, Freon-123, Freon-
124, Freon-125, Freon-143a, Freon-
141b, Freon-142b, Freon-225, Freon-C318, R-502, 1,1,1-trichloroethane, methyl chloride, methylene chloride, ethyl chloride, methyl chloroform, propane, isobutane, n-butane, dimethyl ether, castor oil base Brake fluid, glycol ether brake fluid, borate ester brake fluid, brake fluid for extreme cold, silicone oil brake fluid,
Mineral oil-based brake fluid, power drilling oil, window washer fluid, gasoline, methanol, ethanol,
Low permeability and low vibration of gas and / or liquid (and vaporized gas) such as isoptanol, butanol, hydrogen, nitrogen, oxygen, carbon dioxide, methane, propane, argon, helium, xenon, pharmaceutical agents, etc. Properties, such as excellent dimensional stability at the time of water absorption, for example, including the above-mentioned gas and / or liquid permeation-resistant film, an air bag, a chemical liquid storage tank, a gas storage tank, a cooling liquid tank, Automobile parts such as oil transfer tank, disinfectant tank, transfusion pump tank, fuel tank, fuel tank member, washer liquid tank, washer liquid tank member oil reservoir tank, oil reservoir tank member, etc., parts for medical equipment, and Shampoos, rinses, liquids as tank-shaped molded products as general life appliance parts and their accessories Soap, chemical storage container or its ancillaries such as various pharmaceutical bottles and accessories pump detergents such as bottle-shaped molded article and or their tanks, the bottles
Valves and fittings, such as the attached cut-off valve, included
Parts such as pump gauges and cases, oil tubes
And connecting parts, brake hoses and connecting portions <br/> products, window washer liquid nozzle and hose, cold
Cooler hoses for recirculating water, refrigerant, etc. and their connection parts,
Air-conditioner refrigerant tube and its connection parts, floor heating pipe and its connection parts, fuel filler under
-Pipe, ORVR hose, reserve hose, vent hose
And other fuel tubes and their components and connections
Parts (connectors, etc.) , hoses for fire extinguishers and fire extinguishing equipment, tubes for medical cooling equipment and their connecting parts and valves, and tubes for conveying chemicals and gas,
Applications that require chemical and gas permeability resistance, such as containers for storing chemicals, automotive parts, internal combustion engines, mechanical parts such as power tool housings, and electrical and electronic parts such as calculators, acoustic parts, and fan parts It is effective for various uses such as vacuum insulation boards for refrigerators and cool boxes, medical and food products, household and office supplies, building materials-related parts such as wallpaper, furniture parts, gas bags, balloons, and airships.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme coat ゛ (Reference) C08L 67:00) C08L 67:00) F-term (Reference) 4F071 AA15 AA15X AA28 AA28X AA29 AA29X AA43 AA46 AA80 AD06 AE17 AF08 AF09 AF12 AG28 AH03 AH04 AH05 AH07 AH12 BA01 BB05 BB06 BC01 BC04 BC12 4J002 BB221 BE031 CF042 CF172 CF182 CG002 CL082 DA016 DA026 DA096 DC006 DE096 DE106 DE136 DE146 DE186 DE236 DF016 DG026 DG0006 FA006 DJ0006 FD020 FD030 FD070 FD080 FD090 FD100 FD110 FD130 FD160 FD170 GG01 GN00 GQ00

Claims (8)

[Claims] 1. An ethylene copolymer having an ethylene content of 20 to 60 mol% and a saponification degree of a vinyl acetate component of 80 mol% or more.
In a resin composition (C) comprising 50 to 99.9% by weight of a saponified vinyl acetate copolymer (A) and 50 to 0.1% by weight of a liquid crystal resin (B), (B) is contained in the matrix of (A). And at least 60% by weight of the dispersed particles (B) have a dispersed particle diameter of 0.5α to 1.5α (α is a weight average dispersed particle diameter).
Or a liquid permeation resistant resin composition. 2. The gas and / or liquid permeation resistant resin composition according to claim 1, wherein the weight average dispersed particle size of the liquid crystalline resin (B) is 0.01 to 5 μm. 3. A gas and / or liquid resistant composition obtained by adding 0.5 to 200 parts by weight of a filler to 100 parts by weight of the gas and / or resin composition (C) according to claim 1 or 2. A permeable resin composition. 4. The method according to claim 1, wherein the saponified ethylene-vinyl acetate copolymer (A) and the liquid crystal resin (B) are melt-kneaded at a temperature lower than the melting point of the liquid crystal resin (B). A method for producing a gas and / or liquid permeation-resistant resin composition, comprising producing the gas and / or liquid permeation-resistant resin composition described above. 5. The gas and / or gas according to claim 1,
Or a gas and / or liquid permeation resistant hollow molded article comprising a liquid permeation resistant resin composition. 6. The hollow molded article according to claim 5, wherein the hollow molded article is gaseous and / or
Alternatively, a permeation-resistant hollow molded article used for a liquid transfer line / storage container or an accessory thereof. 7. The gas and / or gas according to claim 1, wherein
Alternatively, a transfer line / storage container obtained by injection-molding a liquid-permeation-resistant resin composition, or an accessory thereof. 8. The gas and / or gas according to claim 1,
Alternatively, a gas and / or liquid permeation resistant film comprising a liquid permeation resistant resin composition.