JP2001131406A - Resin composition for gas- and liquid-barrier molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a gas- and/or liquid-barrier molded product which has an excellent gas- and/or liquid-barrier property and an improved vibration property and creep resistance and is suitable for automobiles, and a molded product. SOLUTION: A resin composition for a gas- and/or liquid-barrier molded product is prepared by compounding from 0.5 to 100 pts.wt. liquid crystal resin (b) having a melting point of from 285 to 340 deg.C with 100 pts.wt. polyamide resin (a).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a variety of gas and / or liquid barriers which are excellent in barrier properties and improve vibration characteristics and creep resistance. TECHNICAL FIELD The present invention relates to a resin composition for molded articles useful for gas and / or liquid molded articles, a molded article thereof, and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in internal combustion engines such as automobiles,
In order to reduce the weight and to cope with environmental problems, replacement of metal parts with resin parts is required. Above all, it is difficult to use resin for parts related to the periphery of the internal combustion engine, the brake mechanism, the driving force transmission mechanism, and the like, because the use environment is severe. Also, fuel, brake oil, coolant,
In consideration of the chemical resistance, a flexible polyamide resin such as polyamide 11 or polyamide 12 has been widely used in the transfer system or storage section of a chemical such as a window cleaning liquid. It is pointed out that if used alone, it is not sufficient for the prevention of permeation of alcohol gasoline, which is required for environmental pollution and improved fuel efficiency, and improvement is desired. In order to do so, various improvements have been attempted.

In recent years, studies have been made to improve gasoline permeability by adding a pretreated inorganic filler having a special shape to a thermoplastic resin, and it is being used for fuel transfer and the like in tube and pipe applications. However, in this case, a problem such as a decrease in toughness occurs, which is not preferable for use in automobiles and the like which require a certain degree of flexibility as well as impact resistance.

Further, from the viewpoint of recyclability and the like, in recent years, studies have been made to improve the fuel permeability by blending a liquid crystal resin with a thermoplastic resin.
No. 37469, for example.

[0005]

However, Japanese Patent Application Laid-Open No.
In the method of 37469, the dimensional stability and gasoline permeability are slightly improved because the liquid crystal resin particles are oriented in the longitudinal direction of the tube, but are not sufficient.
It is not suitable for molded articles because it is difficult to orient the particles only in the longitudinal direction like a tube. Further, when the liquid crystal resin is extremely oriented in order to improve the gas permeability in the thickness direction of the tube in this way, it is not preferable because the liquid crystal resin peels off from the particle interface and causes gas leakage.

[0006] In view of the above, with the aim of improving the above-mentioned conventional problems, it is excellent in gas and / or liquid barrier properties, and improved in vibration characteristics and creep resistance. An object of the present invention is to obtain a resin composition for a barrier molded product that is most suitable for a gas barrier molded product and a molded product thereof.

[0007]

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

That is, the present invention provides a gas and / or liquid comprising (1) 100 parts by weight of a polyamide resin (a) and 0.5 to 100 parts by weight of a liquid crystal resin (b) having a melting point of 285 to 340 ° C. (2) The gas and / or liquid according to the above (1), wherein the melting point of the liquid crystalline resin (b) is 45 ° C. or more higher than the melting point of the polyamide resin (a). Resin composition for barrier molded articles,
(3) The liquid crystalline resin (b) has the following structural units (I), (II),
The resin composition for a gas and / or liquid barrier molded article according to the above (1) or (2), which is a liquid crystalline polyester comprising (III) and (IV).

[0009]

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(Where R ₁ in the formula is

[0011]

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And R ₂ represents one or more groups selected from

[0013]

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And one or more groups selected from In the formula, X represents a hydrogen atom or a chlorine atom. (4) The liquid crystalline resin (b) particles in the resin composition for gaseous and / or liquid barrier molded articles have an elliptical sphere or a flat ellipsoidal sphere, and the aspect ratio thereof (major axis / minor axis, if flat) Has a minor axis in the direction perpendicular to the flat direction.
The resin composition for a gas and / or liquid barrier molded article according to any one of the above (1) to (3), wherein the polyamide resin (a) and the liquid crystal resin (b) are 0 or less. By kneading the liquid crystalline resin (b) at a temperature not lower than the liquid crystal onset temperature and not higher than the melting point,
(4) The method for producing a resin composition for a gas and / or liquid barrier molded article according to any of (1) to (6).
(4) A molded article comprising the resin composition for a gas and / or liquid barrier molded article according to any of (7), (7) the melting point (° C.) of the polyamide resin (a) + 10 ° C. to the melting point (° C.) + 30 ° C. and the liquid crystallinity A method for producing a gas and / or liquid barrier molded product according to the above (6) by molding the resin (b) at a liquid crystal onset temperature (° C.) + 10 ° C. or lower. To provide.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The polyamide resin (a) is a nylon made mainly of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam, ω-laurolactam, tetramethylenediamine, Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, meta Xylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane,
-Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl)
Aliphatic, alicyclic and aromatic diamines such as methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine and aminoethylpiperazine, and adipic acid, speric acid, azelaic acid and sebacine Aliphatics such as acid, dodecane diacid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid , Alicyclic and aromatic dicarboxylic acids. In the present invention, nylon homopolymers or copolymers derived from these raw materials can be used alone or in the form of a mixture.

In the present invention, particularly useful polyamides are polyamides having a melting point of 170 ° C. or higher and excellent in heat resistance and strength. Specific examples include polyundecamide (nylon 11) and polydodeamide (nylon). 1
2), polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide ( Nylon 612), polyhexamethylene adipamide (nylon 6/66), polynonamethylene terephthalamide (nylon 9T), polydodecamide / polyhexamethylene terephthalamide copolymer (nylon 12 /
6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66/6
T), polyhexamethylene terephthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polycaproamide / polyhexamethylene isophthalamide / Polyhexamethylene terephthalamide copolymer (nylon 6 /
6I / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6
I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T
/ 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene terephthalamide) copolymer (nylon 6T / M5T), polyxylylene adipamide (nylon XD6), and mixtures or copolymers thereof. .

Particularly preferred are nylon 11, nylon 12, nylon 6, nylon 66, nylon 610, nylon 9T, nylon 6/66 copolymer, nylon 66/610, nylon 6/12 copolymer, nylon 12 / 6T copolymer, Nylon 6T / 6
Examples include copolymers, nylon 66 / 6T copolymers, nylon 6T / 6I copolymers, nylon 6T / M5T copolymers, and the like. Further, these nylon resins can be molded, heat-resistant, toughness, chemical-resistant, roundness, etc. It is also practically suitable to copolymerize a small amount of a carboxylic acid such as naphthalenedicarboxylic acid or dicarboxybiphenyl, or to use the above-mentioned nylon resin as one kind or a mixture of two kinds according to the required properties of the above.

The degree of polymerization of these polyamide resins is not particularly limited, and preferably has a relative viscosity in a 1% concentrated sulfuric acid solution at 25 ° C. in the range of 2.0 to 8.0,
Those having a range of 3.0 to 7.0 are more preferred, and those having a range of 3.5 to 6.5 are most preferred.

These polyamide copolymers can be obtained by a known method. For example, as a polymerization method, a method such as melt polymerization, interfacial polymerization, solution polymerization, bulk polymerization, or solid phase polymerization is used, and generally, melt polymerization is most suitable. Furthermore, a copolymer can be obtained by introducing the above-mentioned polyamide into an extruder or an injection molding machine and causing a complete or partial exchange reaction.

The liquid crystalline resin (b) has a melting point of 285-34.
0 ° C. is essential, and the melting point is 295-335 ° C.
It is more preferable that the melting point is 310 to 330 ° C.

In the above range, the crystallinity and the packing property of the molecules are high, so that while maintaining the gas and / or liquid barrier properties which are the effects of the present invention, the vibration characteristics,
The creep resistance and the like are specifically improved.

Other structural units are not particularly limited as long as the above requirements are satisfied. Preferred liquid crystalline resins include liquid crystalline polyesters having the following structural units (I), (II), (III) and (IV).

[0024]

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(Where R ₁ in the formula is

[0026]

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R ₂ represents one or more groups selected from

[0028]

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And at least one group selected from the group consisting of In the formula, X represents a hydrogen atom or a chlorine atom. The structural unit (I) is a structural unit generated 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, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-
A structural unit formed from one or more aromatic dihydroxy compounds selected from dihydroxydiphenyl ether,
The structural unit (III) is a structural unit generated from ethylene glycol, and the structural unit (IV) is terephthalic acid, isophthalic acid,
4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid and 4,
The structural units generated from one or more aromatic dicarboxylic acids selected from 4′-diphenyl ether dicarboxylic acids are shown below. Of these, R ₁ is

[0030]

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And R ₂ is

[0032]

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Is particularly preferred.

The above-mentioned structural units (I), (II), (III) and (I) in the liquid crystalline polyester which can be preferably used in the present invention.
The copolymerization amount of V) 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 (I)
II), in the copolymer comprising (IV), the total of the structural units (I) and (II) is preferably 75 to 95 mol% based on the total of the structural units (I), (II) and (III). , 80 to 92 mol% is more preferable. Further, the structural unit (III) is preferably 25 to 5 mol%, more preferably 20 to 8 mol%, based on the total of the structural units (I), (II) and (III). Also,
The molar ratio [(I) / (II)] of the structural unit (I) to (II) is preferably from 75/25 to 95/5, more preferably 7/25.
8/22 to 93/7. Further, it is preferable that the structural unit (IV) is substantially equimolar to the sum of the structural units (II) and (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, a polyesteramide which forms an anisotropic molten phase containing p-iminophenoxy units formed from p-aminophenol in addition to the structural units (I) to (IV) is 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'-diphenyl Aromatic dicarboxylic acids such as dicarboxylic acid, adipic acid, azelaic acid,
Aliphatic dicarboxylic acids such as sebacic acid and dodecanedioic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, chlorohydroquinone, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenylsulfone, 4,4'- Dihydroxydiphenyl sulfide,
Aromatic diols such as 4,4'-dihydroxybenzophenone and 3,4'-dihydroxybiphenyl, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanediol, Aliphatic, alicyclic diols such as 1,4-cyclohexanedimethanol and the like, aromatic hydroxycarboxylic acids such as m-hydroxybenzoic acid, 2,6-hydroxynaphthoic acid and p-aminobenzoic acid;
The copolymer can be further copolymerized within a range that satisfies the essential requirements of the present invention and does not impair the liquid crystallinity.

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. (6) In the presence of 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 (2) or (3). 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 + 10 ° C. is preferably 100 Pa · s
Or less, more preferably 50 Pa · s or less, and most preferably 0.5 to 30 Pa · s.

Here, the melt viscosity is determined at a shear rate of 1,0.
Nozzle diameter 0.5mmφ, nozzle length 1 under the condition of 00 (1 / second)
This is a value measured by a Koka type flow tester using a 0 mm nozzle.

Here, the melting point means the endothermic peak temperature (Tm1) observed when the polymerized polymer 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.

Polyamide resin (a) and liquid crystal resin (b)
The melt viscosity ratio is not particularly limited in order to exert the effects of the present invention. However, the melt viscosity ratio of the polyamide resin (a) under the kneading conditions is adjusted to prevent extremely fine dispersion during kneading. In contrast, the melt viscosity of the liquid crystalline resin (b) is preferably in the range of 0.05 to 1.8,
More preferably 0.1 to 1.5, even more preferably 0.5
In a preferable range, in addition to the gas and / or liquid barrier properties, an effect of improving mechanical properties and the like are obtained, which is preferable.

The melting point of the liquid crystalline resin (b) is required to be 285 to 340 ° C. as described above.
In order to exhibit the characteristics of the present invention, the melting point of the liquid crystalline resin (b) is preferably 45 ° C. or higher than the melting point of the polyamide resin (a), and more preferably the melting point of the liquid crystalline resin (b) is: It is 50 ° C. or higher than the melting point of the polyamide resin (a), and more preferably the melting point of the liquid crystalline resin (b) is 60 ° C. or higher than the melting point of the polyamide resin (a).

Thus, the melting point of the liquid crystalline resin (b) is
If the melting point of the polyamide resin (a) is higher than the melting point of the polyamide resin (a), distribution of the liquid crystal resin particles in the thickness direction will occur in the resulting molded article, and the gas and / or liquid barrier properties which are the effects of the present invention. A material exhibiting heat resistance and a high heat radiation effect can be obtained while maintaining the above.

The liquid crystal onset temperature of the liquid crystalline resin (b) is not particularly limited, but is 220 ° C. or more.
And it is preferable that it is more than melting | fusing point of polyamide resin (a), More preferably, it is 270 degreeC or more, More preferably, it is 290 degreeC or more. The liquid crystal onset temperature was measured using a shear stress heating device (CSS-450) at a shear rate of 1,0.
00 (1 / sec), heating rate 5.0 ° C / min, objective lens 6
The temperature was measured at 0x, and the temperature at which the entire visual field started to flow was defined as the liquid crystal onset temperature.

Polyamide resin (a) of liquid crystalline resin (b)
The compounding amount of the polyamide resin 10 is selected from the viewpoint of not impairing the inherent properties of the polyamide and newly imparting properties such as gas and / or liquid barrier properties and vibration properties.
The amount is 0.5 to 100 parts by weight, preferably 1.0 to 70 parts by weight, more preferably 2 to 50 parts by weight with respect to 0 parts by weight.

In the resin composition for a gas and / or liquid barrier molded article of the present invention, the dispersion form of the liquid crystalline resin (b) dispersed in the polyamide resin (a) is not particularly limited, but the dispersed particles are elliptical spheres. Alternatively, it is preferably a flat ellipsoidal sphere, and the gas and / or liquid barrier properties are best exhibited in the flat direction in most cases in the uniform direction.

The aspect ratio of the liquid crystalline resin particles (b) (major axis / minor axis, but in the case of flattening, the minor axis perpendicular to the flat direction) depends on the gas and / or liquid barrier properties and vibration characteristics. Is more preferably 10 or less, more preferably 1.0 to 8, and still more preferably 1.5 to 5 in order to more clearly exhibit

The number average dispersion diameter (major diameter) of the particles of the liquid crystalline resin (b) is 0.5 to 20 μm in order to further exhibit the gas and / or liquid barrier properties of the present invention.
Is preferably in the range, more preferably 0.8 to
It is 18 μm, more preferably 1.0 to 15 μm.

The method for measuring the number average dispersion diameter of the liquid crystalline resin (b) in the resin composition for a gas and / or liquid barrier molded article is as follows: a section of a core layer portion obtained by cutting the composition in an arbitrary direction. Is observed and photographed with an electron transmission microscope (TEM), and the average value of 100 dispersed particles can be obtained as the number average dispersion diameter in a cross-sectional photograph in the direction in which the longest diameter is observed. The diameter of the dispersed particles is measured in the major axis direction, and when the extruded strand is usually taken after melting and mixing with a cutter or a roller and pelletized, the major axis is observed in the longitudinal direction of the pellet.

It is possible to use a conductive filler and / or a conductive polymer for imparting conductivity to the resin composition for gas and / or liquid barrier molded articles of the present invention. There is no particular limitation, as long as the conductive filler is a conductive filler that is usually used to make a resin conductive. Specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, metal oxide, and conductive metal. Inorganic filler, carbon powder, graphite, carbon fiber, carbon flake, flaky carbon, and the like, which are coated with a conductive 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 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 titanate-based, aluminum-based or silane-based surface treatment agent.

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 substance in the inorganic filler coated with the conductive substance 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 the raw material and the 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 have been 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.

Gas and / or liquid barrier moldings are
Surface smoothness is often required for its use. From such a viewpoint, the conductive filler used in the present invention has a length / diameter ratio of 200 or less in powdery, granular, plate-like, scaly, or resin composition, compared to the fibrous filler having a high aspect ratio. It is preferable that any one of the fibrous forms is used.

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

The conductive filler and / or the conductive polymer may be used in combination of two or more. 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. However, from the viewpoint of the balance between conductivity, fluidity, mechanical strength, and the like, ( The 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).

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 100Ω
· It is more than ¹⁰ cm and not more than 10 ¹⁰ Ω · cm.

In the present invention, a filler can be used to impart mechanical strength and other properties to the resin composition for a gas and / or liquid barrier molded article. Fillers in the form of a plate, a plate, a powder, a granule and the like can be used. Specifically, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, organic fiber such as aromatic polyamide fiber, gypsum fiber,
Fibers and whiskers such as ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, rock wool, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, and silicon nitride whiskers Fillers, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, walsteinite, titanium oxide, zinc oxide, calcium polyphosphate,
A powdery, granular or plate-like filler such as graphite can be used. 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 100 parts by weight of the total of the polyamide resin (a) and the liquid crystal resin (b).
Usually 0.05 to 200 parts by weight, preferably 5 to 200 parts by weight.
100 parts by weight, more preferably 10 to 50 parts by weight.

When a conductive filler is added to impart conductivity, the total amount of the conductive filler and the filler is based on 100 parts by weight of the polyamide resin (a) and the liquid crystal resin (b). Is the addition amount of the conductive filler is 1 to 250
When a part by weight and a conductive polymer are used, the amount of the filler and the conductive polymer are added so as to be within the above ranges.

Further, in the present invention, when it is necessary to further improve the gas and / or liquid barrier properties of a molded article comprising the resin composition for a gas and / or liquid barrier molded article, an acid may be added to increase the interfacial adhesion. An anhydride or a polyepoxy compound can be added. Examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, trimellitic anhydride, , 8-Naphthalic acid,
Examples thereof include phthalic anhydride and maleic anhydride. Among them, succinic anhydride, 1,8-naphthalic anhydride, phthalic anhydride, and maleic anhydride are preferably used. Also,
A 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. Alternatively, a compound obtained by reacting a compound having two or more active hydrogens in one molecule with epichlorohydrin or 2-methylepichlorohydrin is 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, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diethylene glycol, polypropylene glycol, bisphenol A-ethylene oxide adduct, trishydroxyethyl isocyanurate, etc.), amino compounds (eg, ethylenediamine, aniline, etc.) And 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 acid anhydride or polyepoxy compound of the present invention is added in an amount of 0.0 with respect to 100 parts by weight of the polyamide resin in view of the effect of improving gas and / or liquid barrier properties.
1 to 5 parts by weight is preferred, and more preferably 0.05 to 3 parts by weight.
Parts by weight, particularly preferably 0.1 to 2 parts by weight. By using an acid anhydride or a polyepoxy compound, not only the interfacial adhesion is improved, but also the polyamide resin (a)
The distribution width of the dispersed particle diameter and the aspect ratio of the liquid crystalline resin (b) dispersed therein becomes narrow, and as a result, it is possible to obtain a more improved effect of gas and / or liquid barrier properties by adding the liquid crystalline resin. It is.

However, if the amount of the acid anhydride or polyepoxy compound added is too large, gelation due to gas generation or excessive reaction occurs during compounding and extrusion molding, resulting in decomposition and foaming during extrusion, inability to extrude, poor biting, This may cause gas burning of the molded product, and the obtained molded product also tends to have reduced mechanical properties as well as surface appearance.

A copper compound is preferably used in the resin composition for gas and / or liquid barrier molded articles of the present invention 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,
Cupric nitrate, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and the inorganic copper halide and xylylenediamine, 2-
Complex compounds such as mercaptobenzimidazole and benzimidazole are exemplified. Of these, 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 addition amount of the copper compound 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 amount is too large, metal copper is released during melt molding, and the value of the product tends to decrease due to 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.

The resin composition for a gas- and / or liquid-barrier molded article 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.
The addition of an alkoxysilane having a certain functional group is effective in improving mechanical strength, toughness, and the like. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl A) ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2
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 present invention, it is possible to further blend an olefin (co) polymer.

Particularly, at least one selected from an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylate ester from the viewpoint of obtaining an interlayer adhesion in the case of an excellent gas and / or liquid barrier molded article. It is possible to blend an olefin copolymer containing the functional group of

The compounding amount of the olefin copolymer containing at least one functional group selected from the group consisting of an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is determined based on the gas and / or liquid barrier properties. , Vibration characteristics,
From the viewpoint of moldability and the like, the total amount of the polyamide resin (a) and the liquid crystal resin (b) is 100 parts by weight,
A range of parts by weight is selected, preferably from 1 to 100 parts by weight, more preferably from 3 to 50 parts by weight.

Use of an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group. When used in combination with an olefin copolymer containing at least one functional group selected from groups, a gas and / or liquid barrier molded article having excellent smoothness can be obtained, and a more excellent machine can be used. It is effective in obtaining the proper strength and moldability.

When an elastomer which does not contain an epoxy group, an acid anhydride group, a carboxyl group and a salt thereof, and a carboxylic acid ester group is used, the preferable compounding amount is gas and / or liquid barrier properties, surface impact strength, moldability. In terms of
The range of 5 to 200 parts by weight is selected with respect to 100 parts by weight of the total amount of the polyamide resin (a) and the liquid crystalline resin (b), 5 to 100 parts by weight is more preferable, and 10 to 80 parts by weight is further preferable. It is suitable.

When used in combination with a thermoplastic resin having a functional group, particularly from the viewpoint of gas and / or liquid barrier properties, an olefin copolymer having a functional group and an epoxy group, an acid anhydride Product group, carboxyl group and a salt thereof, and a total of elastomers not containing a carboxylate group are a polyamide resin (a) and a liquid crystal resin (b)
200 parts by weight or less, preferably 100 parts by weight or less, more preferably 70 parts by weight or less, based on 100 parts by weight of the total amount of

In the composition of the present invention, other components such as antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites 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 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) A combination of a flame retardant with antimony trioxide, etc.) and other polymers (polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyether sulfone, etc.) can be added.

The method for obtaining the resin composition for gas and / or liquid barrier molded articles of the present invention is not limited as long as the resin composition for gas and / or liquid barrier molded articles specified in the present invention can be obtained. The composition can be prepared using a single-screw extruder equipped with a “Unimelt” type screw, a twin-screw extruder, a kneader of a kneader type, or the like. As a preferable method for appropriately improving the interaction between the polyamide resin (a) and the liquid crystalline resin (b), a suitable shearing force is applied to the resin composition using a twin-screw extruder into which a kneading disk or the like is inserted; It is preferable to perform melt kneading.

The kneading temperature is not particularly limited, but the liquid-crystalline resin (b) should be used in order to sufficiently exhibit the effects of the present invention such as gas and / or liquid barrier properties, vibration properties, and creep resistance. It is preferable to knead the mixture at a temperature equal to or higher than the liquid crystal onset temperature and lower than the melting point. The kneading temperature or the molding temperature described below refers to the resin temperature in extrusion or molding. The resin temperature can be monitored by, for example, the temperature of the resin discharged using a plug-in thermocouple, and the temperature of the resin monitored in this manner is referred to as a resin temperature in the present invention. The resin temperature during kneading is called a kneading temperature, and the resin temperature during molding is called a molding temperature.

When the filler and other additives are added, they may be added at any stage in the preferred method of kneading the polyamide resin (a) and the liquid crystal resin (b). Specifically, polyamide resins and acid anhydrides or polyepoxy compounds, conductive fillers and / or conductive polymers, olefin copolymers containing and / or not containing functional groups, and other additives After melt-kneading, a method of kneading with liquid crystal resin and filler, a method of kneading all components at once, a conductive filler after kneading polyamide resin and acid anhydride or polyepoxy compound, liquid crystal resin once And / or a method of kneading a conductive polymer, an olefin copolymer containing a functional group and / or not containing a functional group, other additive fillers and other additives, once a polyamide resin and an acid anhydride or After kneading a polyvalent epoxy compound and a liquid crystalline resin to obtain a resin composition (A), the obtained resin composition (A) is used to form a conductive filter. High concentration composition of chromatography and / or a conductive polymer such as to create a (master) (B) can be mentioned, it may be any method.

The resin composition for a gas and / or liquid barrier molded article of the present invention can be produced by a master batch method. In that case, a liquid crystal resin (b) is used as a part of the polyamide resin (a) and, if necessary, an olefin resin containing a conductive filler and / or a conductive polymer or a functional group and / or containing no functional group. Mixing a polyamide resin (a) or a polyamide resin (a) and the rest of an acid anhydride or a polyepoxy compound into a master obtained by melt-kneading a copolymer and other additives,
It can be directly subjected to melt molding.

In the production of the resin composition for a gas and / or liquid barrier molded article of the present invention, the properties are more clearly exhibited when a 2 to 50-fold stretching treatment is applied in the monoaxial or biaxial direction after kneading in the production. And preferred. The stretching ratio, stretching speed, stretching method, and the like are not particularly limited, and generally used methods can be preferably used. For example, the most commonly used method is 2
The strand discharged from the axial extruder is applied to a cutter with or without a take-off roller and pelletized. At this time, in the case where the rotation speed of the cutter and the take-off roller are interposed, the stretching process can be performed in one axis direction by adjusting the rotation speed of the take-up roller. Further, the obtained strand was subjected to multiaxial stretching using a heating roller. The liquid crystal resin particles can be flattened, and are preferably used from the viewpoint of gas and / or liquid barrier properties.

The method for molding the resin composition for a gas and / or liquid barrier molded article of the present invention is not limited, and a known method can be used. For example, it can be processed into a three-dimensional molded product by injection molding, extrusion molding, blow molding, compression molding (press molding, injection press molding), or the like. From the viewpoint of exhibiting the characteristics of the present invention, extrusion molding or blow molding is preferred.

The molding temperature is important for exhibiting the gas barrier properties and vibration properties which are the characteristics of the present invention. The molding temperature is from the melting point of the polyamide resin (a) + 10 ° C. to the melting point + 30 ° C. and the liquid crystal resin (b) It is preferable to carry out at a temperature of + 10 ° C. or lower.

In some cases, the characteristics of the present invention are more clearly exhibited by molding the resin composition at a temperature equal to or lower than the minimum processing temperature of the liquid crystal resin (b) alone.

The thus obtained gas and / or liquid barrier molded article is prepared by blending a liquid crystalline resin (b) having a much higher melting point than the polyamide resin (a) and processing it under the above-mentioned preferable conditions. In addition, the liquid crystal resin (b) in the molded product is very distinctive in the form of dispersion.

That is, in the gas and / or liquid barrier molded article, the liquid crystalline resin (b) particles are unevenly dispersed in the thickness direction of the molded article, and at the center in the thickness direction,
The density of the liquid crystalline resin particles is very high, and the ratio of the particle density of the surface layer to the particle density of the central part (surface part / central part) is 0.9 or less for specific improvement of each characteristic. Preferably, it is more preferably 0.3 to 0.9, and still more preferably 0.5 to 0.8.

Due to such a special dispersion form, the resin composition for a gas and / or liquid barrier molded article of the present invention has excellent vibration and creep resistance in addition to excellent gas and / or liquid barrier properties. Since it is improved, it is suitable for a wide range of uses such as electric and electronic parts, mechanical mechanism parts, and automobile parts, and is particularly suitable for use in automobile parts.

Further, the resin composition for a gas and / or liquid barrier molded article of the present invention comprises the resin composition for a gas and / or liquid barrier molded article of the present invention and a resin molded article, film or sheet other than the above. In some cases, it can be used as a laminated product by laminating with metal, paper, cloth including nonwoven fabric, or the like. The method for producing the laminated product is not particularly limited. For example, the gas and / or liquid barrier molded product of the present invention is adhered using a general welding method or an adhesive, or is subjected to insert molding or two-color molding. It may be compounded in a mold by molding or the like. In blow molding, not only ordinary multi-layer simultaneous blowing, but also multilayer blow molding in which one layer is molded and the next layer is molded into an inner layer is used. In addition, in molding a tubular body, the molten resin extruded from the extruder of the number of layers or the number of materials is introduced into one multi-layer tube die, and adhered in the die or immediately after the die exits. Thereby, a multilayer tube can be manufactured. Alternatively, a method may be used in which a single-layer tube is once manufactured, and another layer is laminated inside or outside the tube to manufacture a multilayer tube.

In the case of manufacturing a multilayer tube 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. Is obtained by

The arrangement of each layer in a multilayer molded article using the resin composition for a gas and / or liquid barrier molded article of the present invention is not particularly limited, and all the layers are formed of the gas and / or liquid barrier molded article of the present invention. Or a resin composition for a gas and / or liquid barrier molded article of the present invention in at least one layer, and another thermoplastic resin in another layer. Good. The layer comprising the resin composition for a gas and / or liquid barrier molded article of the present invention may be an outer layer, an inner layer or an intermediate layer,
When imparting conductivity, the innermost layer is preferably used in order to sufficiently exhibit the conductive effect.

The thickness of the layer composed of the resin composition for a gas and / or liquid barrier molded article of the present invention is preferably 0.1 to 5 mm, more preferably 0.5 to 0.5 in a laminated molded article.
２2 mm. In the case of a laminated film, 5 to 5
00 μm is preferable, and more preferably 10 to 200 μm
It is. In the laminated sheet, the thickness is preferably about 0.2 to 5 mm, more preferably 0.5 to 2 mm.

Further, in the composite molded article obtained by two-color molding or insert molding, the composition ratio is such that the resin composition for gas and / or liquid barrier molding of the present invention is:
With respect to other metals, resins, and the like, a preferable composite molded product is obtained in a wide range of 1 to 95%, and its joining or coating form is not particularly limited. In insert molding, the gas and / or gas of the present invention is used. The resin composition for a liquid barrier molded article may be a mold insert component or a coating or joining component. In the two-color molding, a method of using the resin composition for a gas and / or liquid barrier molded article of the present invention at a site where gas and / or liquid barrier properties are required using another thermoplastic resin as a base is preferably used. However, the resin composition for a gas and / or liquid barrier molded article of the present invention has a surface property sufficiently retaining the properties of the nylon resin (a). Is obtained.

The thermoplastic resin other than the resin composition for a gas and / or liquid barrier molded article of the present invention used herein includes saturated polyester resin, polysulfone resin, and the like.
Polytetrafluoroethylene resin, polyetherimide resin,
Polyamide imide resin, polyamide resin, polyphenylene ether resin, polyimide resin, polyether sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, thermoplastic polyurethane resin, polyolefin resin, ABS resin,
Polyamide elastomers, polyester elastomers, etc. 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 impart desired physical properties. It is possible.

The gas and / or liquid barrier molded article of the present invention thus obtained is excellent in gas and / or liquid barrier properties, and improved in vibration characteristics and creep resistance. (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,
Isopropanol, butanol, nitrogen, oxygen, carbon dioxide, methane, propane, argon, helium, xenon, pharmaceutical agents, etc.) Pipes used for transport lines, storage tanks, pots, packings, flanges, valves, cocks, etc. for the above chemicals It is effective as automotive parts such as those accessory parts, electric / electronic parts, and parts for medical instruments. Specifically, a coolant tank, an oil transfer tank, a disinfectant tank, a blood transfusion pump tank, a fuel tank, a fuel tank member, a washer liquid tank, a washer liquid tank member, an oil reservoir tank, an oil reservoir tank member, and the like. It is effective for tank-shaped molded articles and their accessories as automotive parts, medical equipment parts, and general living equipment parts. In particular, the gas and / or liquid barrier molded article of the present invention is preferably applied to internal combustion engines such as automobiles and peripheral uses thereof, such as fuel tubes, tanks, and their accessories, which can sufficiently exhibit the above characteristics.

[0100]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Reference Example 1 (Polyamide resin) A-1: ε-caprolactam was polymerized by a conventional method to obtain nylon 6 pellets. The logarithmic viscosity of this polyamide was 4.20 and the melting point was 222 ° C.

A-2: Equimolar salt of hexamethylenediamine-adipic acid 20% by weight, ε-caprolactam in 80%
% By weight of a mixed aqueous solution (solid raw material concentration: 60% by weight) was charged into a pressure polymerization vessel, and the temperature was raised with stirring, and the steam pressure was 17 kg / cm.
After reacting for 1.5 hours at ² , the pressure was gradually released over about 2 hours, and further reacted for about 30 minutes under a nitrogen stream at normal pressure to obtain a polyamide resin having a relative viscosity of 4.09 and a melting point of 192 ° C.

Reference Example 2 (Liquid crystal resin) B-1: 994 parts by weight of p-hydroxybenzoic acid, 4,4
126 parts by weight of '-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, 216 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g, and 960 parts of acetic anhydride
A part by weight was charged into a reaction vessel equipped with a stirring blade and a distilling tube, and as a result of polymerization, 80 mole equivalents of aromatic oxycarbonyl units, 7.5 mole equivalents of aromatic dioxy units, and 12.5 moles of ethylenedioxy units Equivalent, 20 mol equivalent of aromatic dicarboxylic acid unit, melting point 314 ° C., liquid crystal onset temperature 29
A liquid crystalline resin having a melt viscosity of 21 Pa · s at 3 ° C. and 324 ° C. (orifice 0.5φ × 10 mm, shear rate 1,000 (1 / sec)) was obtained.

B-2: 907 parts by weight of p-hydroxybenzoic acid, 457 parts by weight of 6-hydroxy-2-naphthoic acid and 873 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube to conduct polymerization. As a result, the melt viscosity at a melting point of 283 ° C. consisting of 100 molar equivalents of aromatic oxycarbonyl units, a liquid crystal onset temperature of 233 ° C. and 293 ° C. was 50 Pa · s
(Orifice 0.5φ × 10mm, Shear speed 1,000
(1 / sec)) was obtained.

B-3: p-hydroxybenzoic acid 839
Parts by weight, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, intrinsic viscosity of about 0.6 d
1 / g of 432 parts by weight of polyethylene terephthalate and 682 parts by weight of acetic anhydride were charged into a reaction vessel equipped with a stirring blade and a distilling tube, and as a result of polymerization, 72.5 mole equivalents of aromatic oxycarbonyl units were obtained. Melting point 232 consisting of 7.5 molar equivalents of aromatic dioxy units, 20 molar equivalents of ethylenedioxy units, and 27.5 molar equivalents of aromatic dicarboxylic acid units
° C, liquid crystal onset temperature 207 ° C, melt viscosity 47P at 242 ° C
a · s (orifice 0.5φ × 10mm, shear rate 1,0
00 (1 / sec)).

Examples 1 to 5, Comparative Examples 1 to 5 Polyamide resins (A-1, A-
2) 100 parts by weight of liquid crystalline resin (B-1 to B-
3) Dry-blending the filler and other additives, and melt-kneading at a kneading temperature shown in Table 1 with a PCM30 type twin screw extruder (Ikegai Iron and Steel) incorporating a kneading disk in a screw pattern to obtain a resin composition. Obtained. The obtained composition was pelletized with a take-off cutter through two upper and lower heating rollers, and then vacuum dried at 80 ° C. for 10 hours.
It is supplied to Sumitomo Nestar injection molding machine Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and the molding temperature is set to 250 ° C. and the mold temperature is set to 80 ° C. Molded articles for each test were molded. It was evaluated by the following method.

(1) Dispersion State The aspect ratio of the liquid crystalline resin (b) in the polyamide resin (a) was determined by cutting the central part of the pellet obtained by kneading and pelletizing in the longitudinal direction. (Prepared in the thickness direction and the width direction, respectively) were observed and photographed with an electron transmission microscope (TEM). In this cross-sectional photograph, the aspect ratio (major axis / minor axis, with respect to flat elliptical spherical particles, the minor axis in the vertical direction of the flat direction) was calculated for 50 liquid crystal resin particles, and the average was evaluated for 50 particles. (Large axis / width direction short axis ratio = width direction aspect ratio).

(2) Barrier Property (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 the tube and controlling the size,
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 was further cut into a length of 30 cm, one end of the tube was sealed, and a gasoline mixture of a commercial regular gasoline and methyl alcohol and ethyl alcohol mixed at a weight ratio of 70:20:10 was put therein, 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., and the alcohol gasoline permeability was evaluated based on the change in weight.

(3) Vibration Characteristics A test piece having a size of 220 mm × 12.7 mm × 3.2 mm was formed, and a magnetic steel having a thickness of 8 mmφ × 0.3 mm was formed on the obtained test piece at a position of 50 and 150 mm from the fixed portion. Glued and set in a high / low temperature bath to determine the loss coefficient at the primary resonance frequency (power amplifier (B & K type 2706), preamplifier (B & K type 2639S type) and 2-channel F
FT analyzer (Model 2034 manufactured by B & K) is used). The evaluation was performed based on the number of vibrations until the amplitude attenuated to 1/10.

(4) Creep resistance

In the above molding machine, the AS of the distance between the gauges was 1/2.
A test piece of TM1 dumbbell (thickness: 3.12 mm) was prepared and subjected to a test under the conditions of a tensile stress of 2 MPa and 80 ° C. for 500 hours.

[0112]

[Table 1]

From the results shown in Table 1, the resin composition for a gas and / or liquid barrier molded article of the present invention has extremely excellent gas and / or liquid barrier properties, and has improved vibration characteristics and creep resistance. Therefore, a gas that is suitable for use in automotive parts where these characteristics are required, especially for parts requiring fuel and oil gas and / or liquid barrier properties, such as fuel transfer pipes, oil reservoir tanks and their accessories, etc. And / or a liquid barrier molded article can be obtained.

[0114]

As described above, the resin composition for a gas and / or liquid barrier molded article of the present invention has excellent barrier properties against various gases and / or liquids, and has improved vibration characteristics and creep resistance. In addition, a resin composition useful for many gaseous and / or liquid barrier uses and a molded product thereof, including those for automobiles where these properties are required, can be obtained, especially for internal combustion engines exposed to vibrations such as automobiles. It is preferably applied to fuel pipes and tanks and their peripheral parts.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 101/12 101/12 F term (Reference) 4F071 AA43 AA43X AA54 AA84 AD02 AF08 AF09 AF13 AG21 AH05 BA01 BB05 BB06 BC04 4J002 CF162 CH062 CH092 CJ002 CL011 CL031 CL051 CL082 FD020 FD030 FD060 FD110 FD130 FD160 FD170 GB01 GN00 GQ00 4J029 AA05 AC02 AE01 BA03 BB05A BB05B BB10A BB10B BB13A BC05A BC06A BF14A CB05A CB06A CB10A CB12A CB12B CC06A CF08 EB05A HA01 HB01 JB163 KD02 KE02 KE06

Claims (7)

[Claims] (1) 100 parts by weight of a polyamide resin (a) are mixed with a liquid crystal resin (b) having a melting point of 285 to 340 ° C.
A resin composition for a gas and / or liquid barrier molded product, which is blended with 0 parts by weight. 2. The resin composition for gas and / or liquid barrier molded articles according to claim 1, wherein the melting point of said liquid crystalline resin (b) is higher than that of the polyamide resin (a) by 45 ° C. or more. . 3. The liquid crystalline resin (b) comprises the following structural unit (I):
The resin composition for a gas and / or liquid barrier molded article according to claim 1 or 2, which is a liquid crystalline polyester composed of (II), (III) and (IV). Embedded image (Where R ₁ in the formula is And R ₂ represents one or more groups selected from And at least one group selected from In the formula, X represents a hydrogen atom or a chlorine atom. ) 4. The liquid crystalline resin (b) particles in the resin composition for a gas and / or liquid barrier molded article have an elliptical sphere or a flat elliptical sphere, and have an aspect ratio (major axis / minor axis,
However, the resin composition for gas and / or liquid barrier molded articles according to any one of claims 1 to 3, wherein when flat, the minor axis in the direction perpendicular to the flat direction is 10 or less. 5. The gas according to claim 1, wherein the polyamide resin (a) and the liquid crystal resin (b) are kneaded at a temperature not lower than the liquid crystal onset temperature and not higher than the melting point of the liquid crystal resin (b). And / or a method for producing a resin composition for a liquid barrier molded article. 6. The gas and / or gas according to claim 1, wherein
Or a molded article comprising the resin composition for a liquid barrier molded article. 7. The melting point (° C.) of the polyamide resin (a) +10
7. The gas and / or liquid barrier molded article according to claim 6, which is formed by molding at a temperature of from 0 ° C to a melting point (° C) + 30 ° C and a liquid crystal onset temperature (° C) of the liquid crystalline resin (b) + 10 ° C or less. A method for producing a barrier molded product, characterized by comprising: