JP2010248417A - Thermoplastic resin composition with excellent barrier property - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition with excellent mechanical properties including barrier property, strength, impact resistance and elongation, further with excellent heat resistance. <P>SOLUTION: The thermoplastic resin composition includes 0.1 to 10 pts.mass of (B) a carbodiimide compound having two or more carbodiimide groups and 100 pts.mass of (A) a polyamide resin composition including 5-60 mass% of (a-1) a polyamide resin with 70 mol% or more of a diamine constituent unit derived from a methaxylylene diamine and 70 mol% or more of a dicarboxylic acid constituent unit derived from a 4-20C α,ω-straight chain aliphatic dicarboxylic acid, 5-60 mass% of (a-2) a nylon 11, and 5-50 mass% of (a-3) a polyamide having a 110°C or higher glass transition point. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a thermoplastic resin composition having excellent barrier properties and strength, mechanical properties such as impact resistance and elongation, and further excellent heat resistance. More particularly, the present invention relates to a thermoplastic resin composition having excellent barrier properties and heat resistance as a container and tube for alcohol-containing fuel, and a component material.

Various types of resin materials are used for fuel storage containers and tubes from the viewpoints of weight reduction, elimination of rust prevention treatment, improvement in shape flexibility, reduction of processing steps, and full automation of manufacturing. In particular, polyamides such as nylon 11 and nylon 12 are used for various automobile parts such as tubes, hoses, and fuel parts. This polyamide is light in weight, does not generate rust, has a good fuel barrier property with respect to ordinary gasoline, and has excellent characteristics required for these applications, and is therefore widely used.
However, in recent years, from the viewpoint of exhaustion of gasoline resources and environmental conservation, studies are being made to use a mixed fuel in which alcohols such as ethanol are added to gasoline, but polyamide has a remarkably low barrier property to alcohols. The permeation amount of mixed gasoline reaches 50 to 60 times that of normal gasoline. Therefore, it is difficult to fully meet regulations that will be strengthened in the future, and a material with higher barrier performance is desired.
On the other hand, it is known that heat resistance is improved by adding polycarbodiimide to a thermoplastic resin (see Patent Document 1). In addition, it is known that hydrolysis resistance, oil resistance, and metal halide resistance can be improved by blending an aliphatic carbodiimide compound with polyamide (see Patent Document 2). However, these documents do not describe improvement in mechanical properties such as fuel barrier properties, strength, impact resistance, and elongation. Further, a polyamide resin (a-1) composed of a diamine mainly composed of metaxylylenediamine and a dicarboxylic acid mainly composed of α, ω-linear aliphatic dicarboxylic acid, and nylon 11 and / or nylon 12 (a A thermoplastic resin composition in which a carbodiimide compound having two or more carbodiimide groups is contained in the polyamide resin composition comprising -2) is disclosed (see Patent Document 3).

Japanese Patent Laid-Open No. 02-175757 Japanese Patent Laid-Open No. 11-343408 JP 2008-133455 A

Although the composition in the above-mentioned Patent Document 3 is excellent in fuel permeability and mechanical strength at room temperature, a molded article made of this composition may be exposed to high temperatures, and in some cases, its mechanical strength is reduced, Sometimes it was not practical.
The object of the present invention is to provide a thermoplastic resin composition excellent in mechanical properties such as barrier properties and strength, impact resistance and elongation, and further in heat resistance, in particular, a container and a tube for an alcohol-containing fuel, from the above situation. An object of the present invention is to provide a thermoplastic resin composition having excellent barrier properties and heat resistance as a component material.

  As a result of intensive investigations to achieve the above object, the present inventors have found that a specific polyamide resin composition comprising a barrier polyamide having a metaxylylene skeleton and nylon 11 and a polyamide having a glass transition point of 110 ° C. or higher has a carbodiimide compound. It has been found that a thermoplastic resin composition suitable for the above-mentioned purpose can be obtained by containing, and the present invention has been completed.

  That is, in the present invention, 70 mol% or more of the diamine structural unit is derived from metaxylylenediamine, and 70 mol% or more of the dicarboxylic acid structural unit is an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. The polyamide resin (a-1) derived from, the nylon 11 (a-2), and the polyamide (a-3) having a glass transition point of 110 ° C. or higher, wherein the component (a-1) is 5 to 60% by mass, The carbodiimide having two or more carbodiimide groups with respect to 100 parts by mass of the polyamide resin composition (A) in which the component (a-2) is 5 to 60% by mass and the component (a-3) is 5 to 50% by mass. The present invention relates to a thermoplastic resin composition containing 0.1 to 10 parts by mass of the compound (B), and a molded body using the thermoplastic resin composition.

In the thermoplastic resin composition of the present invention, a carbodiimide compound is added to a polyamide having a barrier property polyamide having a metaxylylene skeleton, a nylon 11 having a functional group that reacts with a carbodiimide group, and a polyamide having a glass transition point of 110 ° C. or higher. By doing so, the polyamide and the compound having a functional group that reacts with the carbodiimide group are bonded via the carbodiimide compound, or each of the polyamide and the compound having a functional group that reacts with the carbodiimide group is a carbodiimide compound. By reacting with Nylon 11 and Nylon 12 having barrier strength polyamide having a metaxylylene skeleton, which has been difficult in the past, and Nylon 11 and Nylon 12 having excellent impact strength with flexibility. Melt mixing is possible Excellent barrier properties, strength and impact resistance, the thermoplastic resin composition is obtained further has a heat resistance.
Therefore, the thermoplastic resin composition of the present invention is excellent in barrier properties, strength and impact resistance, heat resistance, particularly barrier properties of alcohol-containing fuel, and can be used for various molded products such as fuel containers, tubes, parts, and the like. Preferably used.

The polyamide resin composition (A) in the thermoplastic resin composition of the present invention is a polyamide resin comprising a diamine structural unit (structural unit derived from diamine) and a dicarboxylic acid structural unit (structural unit derived from dicarboxylic acid). 70 mol% or more, preferably 80 mol% or more of the diamine structural unit is derived from metaxylylenediamine, and 70 mol% or more, preferably 80 mol% or more of the dicarboxylic acid structural unit is an α having 4 to 20 carbon atoms. Polyamide resin (a-1) derived from ω-linear aliphatic dicarboxylic acid is used.
The polyamide resin (a-1) comprises 70 mol% of a diamine component containing metaxylylenediamine at 70 mol% or more, preferably 80 mol% or more, and an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Above, preferably obtained by polycondensation of a dicarboxylic acid component containing 80 mol% or more.

Examples of diamines other than metaxylylenediamine used as a raw material (diamine component) for the polyamide resin (a-1) include tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, and octamethylenediamine. , Nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and other aliphatic diamines, 1,3-bis (aminomethyl) ) Cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) Alicyclic diamines such as lopan, bis (aminomethyl) decalin (including structural isomers), bis (aminomethyl) tricyclodecane (including structural isomers), bis (4-aminophenyl) ether, para Examples include diamines having an aromatic ring such as phenylenediamine, paraxylylenediamine, bis (aminomethyl) naphthalene (including structural isomers), and the like, and one or a mixture of two or more can be used. .

  In the present invention, examples of the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms include succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, adipic acid, sebacic acid, undecanedioic acid, and dodecane. Aliphatic dicarboxylic acids such as diacids can be exemplified, and one kind or a mixture of two or more kinds can be used. Among these, adipic acid is preferred.

In the present invention, the range of 30 mol% or less (not including 0 mol%) of the dicarboxylic acid structural unit is more preferably derived from isophthalic acid, more preferably 0 to 25 mol%, and still more preferably 5 to 20 mol. % Range.
When isophthalic acid is included, the melting point of the resulting polyamide resin is lower than when only α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used, and molding can be performed at a lower temperature, reducing production energy and molding. Not only can the cycle be shortened, but the melt viscosity is increased and the moldability of the resin against drawdown is improved, but the barrier properties of the thermoplastic resin composition are reduced.

Examples of the dicarboxylic acid component other than the α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms and isophthalic acid include phthalic acid compounds such as terephthalic acid and orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,3 -Naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-naphthalene Dicarboxylic acids, naphthalene dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid isomers, monocarboxylic acids such as benzoic acid, propionic acid and butyric acid; and many such as trimellitic acid and pyromellitic acid Carboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride Can.

The polyamide resin (a-1) comprises a diamine component containing 70 mol% or more of metaxylylenediamine and a dicarboxylic acid component containing 70 mol% or more of an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms. Although it is obtained by polycondensation, its production method is not particularly limited, and it is produced by a conventionally known method such as atmospheric pressure melt polymerization or pressure melt polymerization, and polymerization conditions. For example, metaxylylenediamine and adipic acid or a nylon salt consisting of metaxylylenediamine, adipic acid and isophthalic acid is heated in the presence of water under pressure, and melted while removing the added water and condensed water. It is manufactured by a method of polymerizing in a state. Further, it is also produced by a method in which metaxylylenediamine is directly added to molten adipic acid or a mixture of adipic acid and isophthalic acid and polycondensed under normal pressure. In this case, in order not to solidify the reaction system, metaxylylenediamine is continuously added, and while raising the reaction system so that the reaction temperature therebetween is equal to or higher than the melting point of the generated oligoamide and polyamide, Polycondensation proceeds.

When the polyamide resin (a-1) is obtained by polycondensation, the polycondensation reaction system includes lactams such as ε-caprolactam, ω-laurolactam, ω-enantolactam, 6-aminocaproic acid, 7-aminoheptanoic acid. , 11-aminoundecanoic acid, 12-aminododecanoic acid, 9-aminononanoic acid, amino acids such as paraaminomethylbenzoic acid and the like may be added within a range that does not impair the performance.

The polyamide resin (a-1) may be further heat-treated to increase the melt viscosity. As a heat treatment method, for example, using a batch-type heating device such as a rotating drum, in an inert gas atmosphere or under reduced pressure, it is heated gently in the presence of water, and crystallized while avoiding fusion. Thereafter, a method of further heat treatment; heating in an inert gas atmosphere using a grooved stirring and heating device, and after crystallization, heat treatment in an inert gas atmosphere using a hopper-shaped heating device A method of performing a heat treatment using a batch-type heating device such as a rotating drum after crystallization using a groove type stirring and heating device. Among them, a method of performing crystallization and heat treatment using a batch heating apparatus is preferable. The heat treatment conditions are as follows: the temperature is raised from 70 to 120 ° C. in the presence of 1 to 30% by mass of water with respect to the polyamide resin obtained by melt polymerization, and over 0.5 to 4 hours. Then, in an inert gas atmosphere or under reduced pressure, the temperature ranges from [melting point of polyamide resin obtained by melt polymerization—50 ° C.] to [melting point of polyamide resin obtained by melt polymerization—10 ° C.]. Conditions for heat treatment for 12 hours are preferred.

The melting point of the polyamide resin (a-1) is preferably controlled in the range of 160 ° C to 240 ° C, more preferably 170 to 235 ° C, and further preferably 180 to 230 ° C.

It is preferable that the glass transition point of a polyamide resin (a-1) is the range of 80-130 degreeC. By setting the glass transition point of polyamide to 80 ° C. or higher, a polyamide having excellent barrier properties at high temperatures can be obtained.

As the polyamide resin (a-1), those having a terminal amino group concentration of less than 40 μequivalent / g, preferably 10 to 30 μequivalent / g, and a terminal carboxyl group concentration of 40 to 100 μequivalent / g are suitably used. By setting the terminal amino group concentration and the terminal carboxyl group concentration within the above ranges, the resulting barrier layer is not colored yellow.

The polyamide resin (a-1) may contain a phosphorus compound in order to increase processing stability during melt molding or to prevent the polyamide resin from being colored. As the phosphorus compound, a phosphorus compound containing an alkali metal or an alkaline earth metal is preferably used. Examples thereof include phosphates such as sodium, magnesium and calcium, hypophosphites and phosphites, and alkali metals. Alternatively, a material using an alkaline earth metal hypophosphite is preferably used because it is particularly excellent in the anti-coloring effect of the polyamide. The concentration of the phosphorus compound in the polyamide (A) is desirably 200 ppm or less, preferably 160 ppm or less, more preferably 100 ppm or less as phosphorus atoms.
In addition to the above phosphorus compounds, the polyamide resin (a-1) includes a lubricant, a matting agent, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, and a nucleating agent as long as the effects of the present invention are not impaired. Additives such as plasticizers, flame retardants, antistatic agents, anti-coloring agents and anti-gelling agents can also be added, but not limited to those shown above, various materials can be mixed Also good.

  As nylon 11 (a-2), 11-aminoundecanoic acid or undecane lactam is selected, and those excellent in melt molding are preferred. The viscosity of the relative viscosity polyamide measured at 25 ° C. with a 98% concentrated sulfuric acid solution is in the range of 1.5 to 7, preferably in the range of 1.8 to 5, more preferably in the range of 2 to 4. .

The polyamide (a-3) having a glass transition point of 110 ° C. or higher is not particularly limited, but nylon 46, nylon 6T, nylon 6I, nylon 6IT, nylon 9T, nylon 9MT, nylon 66 / 6T, nylon 66 / 6I, nylon 6 / 6T, nylon 6I / 6T, nylon 66 / 6T / 6I, nylon 6T / 5MT, nylon 6T / 12 and the like are preferable, and nylon 6IT is particularly preferable.

The polyamide resin (a-1) reacts with the carbodiimide group by adding the carbodiimide compound (B) to the compound having a functional group that reacts with the carbodiimide group and melt-kneading the compound. Affinity with polyamide having a functional group is improved.

The polyamide resin composition (A) used in the present invention comprises a polyamide resin (a-1), nylon 11 (a-2), and a polyamide (a-3) having a glass transition point of 110 ° C. or higher. -1) 5 to 60% by mass of component, (a-2) 5 to 60% by mass of component, (a-3) 100 parts by mass of polyamide resin composition (A) whose component is 5 to 50% by mass The carbodiimide compound (B) having two or more carbodiimide groups in the molecule is 0.1 to 10 parts by mass, and the component (a-1) is 5 to 60% by mass, and the component 5 is (a-2). ~ 60 mass%, (a-3) component 5-50 mass%, preferably (a-1) component 10-50 mass% and (a-2) component 10-50 mass% (a) -3) Component 10 to 40% by mass, more preferably (a-1) Component 15 to 45 The amount% and component (a-2) 15 to 45 wt% and (a-3) is made of components 15 to 35 wt%. By setting the polyamide resin of the component (a-1) to 5% by mass or more, sufficient barrier properties are obtained, and by setting it to 60% by mass or less, strength and impact resistance are excellent. The nylon 11 as the component (a-2) has excellent mechanical strength when it is 5% by mass or more, and has excellent barrier properties when it is 60% by mass or less. Moreover, (a-3) component will be excellent in heat resistance by adding 5-50 mass%.

The water content of the polyamides (a-1), (a-2) and (a-3) used is preferably 0.3% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0.05% by mass or less. It is desirable to dry within this range as necessary. By setting the moisture to 0.3% by mass or less, the reaction between the carbodiimide group and moisture does not proceed, so that a thermoplastic resin composition having excellent characteristics can be obtained without causing poor extrudability. Can do. When drying a polyamide resin composition (A), it can carry out by a well-known method. For example, the polyamide resin composition (A) is charged into a heatable tumbler (rotary vacuum tank) with a vacuum pump or a vacuum dryer, and heated at a temperature not higher than the melting point of the polymer, preferably not higher than 160 ° C., under reduced pressure. However, it is not limited to this. The water content can be obtained by measuring the amount of water that volatilizes in 30 minutes at a temperature 5 ° C. lower than the melting point of the polyamide in a nitrogen stream at a temperature lower than the melting point of the polyamide.

In the present invention, the carbodiimide compound (B) having two or more carbodiimide groups added to the polyamide resin composition (A) is an aromatic, aliphatic or alicyclic polycarbodiimide compound produced by various methods. Is mentioned. Among these, an aliphatic or alicyclic polycarbodiimide compound is preferably used from the viewpoint of melt kneading at the time of extrusion, and an aliphatic polycarbodiimide compound is more preferably used.
These carbodiimide compounds (B) can be produced by decarboxylation condensation reaction of organic polyisocyanate. For example, a method of synthesizing various organic polyisocyanates by decarboxylation condensation reaction at a temperature of about 70 ° C. or higher in an inert solvent or without using a solvent in the presence of a carbodiimidization catalyst can be exemplified. .

As organic polyisocyanate which is a synthesis raw material of the carbodiimide compound (B), for example, various organic diisocyanates such as aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, and mixtures thereof can be used. Specific examples of the organic diisocyanate include 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2 , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate, methylcyclohexane diisocyanate, tetramethylxylylene Range isocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropylbenzene-2,4-di It can be exemplified isocyanate and the like.

An end-capping agent such as monoisocyanate can be used to seal the ends of the carbodiimide compound (B) and control the degree of polymerization. Examples of the monoisocyanate include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate.

In addition, as terminal blocker, it is not limited to said monoisocyanate, What is necessary is just an active hydrogen compound which can react with isocyanate. Examples of such active hydrogen compounds include aliphatic, aromatic, and alicyclic compounds, methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, polypropylene having —OH groups. Secondary amines such as glycol monomethyl ether, diethylamine and dicyclohexylamine, primary amines such as butylamine and cyclohexylamine, carboxylic acids such as succinic acid, benzoic acid and dichlorohexanecarboxylic acid, thiols such as ethyl mercaptan, allyl mercaptan and thiophenol And compounds having an epoxy group.

Examples of the carbodiimidization catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide, 3- Metal catalysts such as phospholene oxides such as methyl-2-phospholene-1-oxide and their 3-phospholene isomers, tetrabutyl titanate and the like can be used, and among these, from the viewpoint of reactivity, 3 -Methyl-1-phenyl-2-phospholene-1-oxide is preferred.

In the thermoplastic resin composition of the present invention, the carbodiimide compound (B) may react with the polyamide resin composition (A) or the polyamide resin (a-1). By melt-kneading the polyamide resin (a-1), nylon 11 and / or nylon 12 (a-2), and the carbodiimide compound (B), the polyamide resin (a- 1) and nylon 11 and / or nylon 12 (a-2) are combined, or (II) polyamide resin (a-1) and nylon 11 and / or nylon 12 (a-2), respectively By reacting with the carbodiimide compound (B), the affinity between the polyamide resin (a-1) and nylon 11 and / or nylon 12 (a-2) is improved via the carbodiimide compound (B). , Barrier polyamide having a metaxylylene skeleton and nylon 12 having flexibility and excellent impact strength, which has been difficult in the past. It enables melt mixing, barrier, thermoplastic resin composition excellent in strength and impact resistance can be obtained.

The thermoplastic resin composition of the present invention is 0.1 to 10 parts by weight, preferably 0.2 to 8 parts by weight, more preferably 100 parts by weight of the polyamide resin composition (A). , 0.3 to 5 parts by mass.

The relative viscosity of the thermoplastic resin composition of the present invention is preferably 1.7 to 4.0, more preferably 1.9 to 3.8. The relative viscosity is measured by the method described later.

After melt-kneading the thermoplastic resin composition of the present invention, various molded products can be obtained by extrusion molding or injection molding. When the added amount of the carbodiimide compound (B) is 0.1 parts by mass or more, kneadability is sufficient, and problems such as discharge unevenness during extrusion do not occur. By setting the addition amount to 10 parts by mass or less, significant thickening occurs and extrusion does not become difficult.

The thermoplastic resin composition of the present invention includes reinforcing fibers such as glass fibers, crystal nucleating agents, lubricants, mold release agents, antioxidants, processing stabilizers, heat stabilizers, and the like unless the object of the present invention is impaired. Agents, ultraviolet absorbers, layered silicates, inorganic or organic metal salts such as Co, Mn and Zn, complexes and the like can be added.

Examples of the method of melt-kneading the polyamide resin composition (A) and the carbodiimide compound (B) include methods of melt-kneading using various commonly used extruders such as a single-screw or twin-screw extruder. Among these, the method using a twin screw extruder is preferable from the viewpoint of productivity, versatility, and the like.

At that time, it is preferable to adjust the melt-kneading temperature to 200 to 300 ° C. and the residence time to 10 minutes or less, and the screw has at least one reverse screw element and / or kneading disk, It is preferable to carry out a partial retention.
By setting the melt-kneading temperature in the above range, the extrusion kneading defect and decomposition do not occur.

  Using the thermoplastic resin composition of the present invention, it can be molded into various forms such as tubes, hoses, parts, etc. by a conventionally known molding method. For example, molding methods such as molding by an extruder, injection molding, press molding, direct blow molding, rotational molding, sandwich molding, and two-color molding can be exemplified.

The molded body of the present invention is formed using the thermoplastic resin composition, and has a layer excellent in barrier properties, strength, and impact resistance. The molded body of the present invention may be a single layer or a multilayer, but particularly from the viewpoint of the strength of the molded body, it contains at least one thermoplastic resin composition layer, and includes polyolefin, polystyrene, polyester, polycarbonate, polyamide, or fluorine resin. A multilayer molded body in which at least one reinforcing layer composed of, for example, is laminated is preferable.
As the polyolefin used in the reinforcing layer, two types selected from linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, ultra high molecular weight high density polyethylene, polypropylene, ethylene, propylene, butene, etc. Examples of the above olefin copolymers, and mixtures thereof, modified fluororesins, and polyamides. The polyolefin, polyester, polycarbonate, polyamide and fluorine resin exemplified in the reinforcing layer are mixed with each other, mixed with other resins such as elastomers, and other additives such as carbon black and flame retardants. It is also possible to use a mixture.

In the molded article of the present invention, an adhesive resin layer (adhesive layer) can be provided between each layer constituting the multilayer molded article, such as a thermoplastic resin composition layer and a reinforcing layer. Examples of the adhesive resin constituting the adhesive layer include, for example, a modified polyethylene or polypropylene, or an olefin such as ethylene, propylene, or butenes when the thermoplastic resin composition layer and a reinforcing layer made of polyolefin are adhered. Copolymers or the like can be used. When the thermoplastic resin composition layer and a reinforcing layer made of polyester or polycarbonate are bonded, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer alkali or alkaline earth metal crosslinked body, and An ethylene-acrylic acid ester-based copolymer and the like can be exemplified, but are not particularly limited.

The thickness of each layer in the multilayer molded body is selected according to the shape of the multilayer molded body. The thermoplastic resin composition layer has an average of 0.005 to 5 mm, the reinforcing layer has an average of 0.005 to 10 mm, and an adhesive layer. Is preferably 0.005 to 5 mm on average.

Hereinafter, the present invention will be described specifically by way of examples.
In the following examples and comparative examples, the polyamide resin composition (A), the thermoplastic resin composition, and the film molded body were evaluated by the following methods.
(1) Tensile properties A strip-shaped test piece having a width of 10 mm and a length of 120 mm was prepared from a film in an environment of 23 ° C. and 50% RH, and a strograph V1-C (manufactured by Toyo Seiki Seisakusho) was used. The fracture strength (MPa), fracture elongation (%), and elastic modulus (GPa) were measured in accordance with ASTM-D882 under conditions of a distance between chucks of 50 mm and a tensile speed of 50 mm / min.
(2) Impact punching strength In an environment of 23 ° C. and 50% RH, using a film impact tester (ITF-60, manufactured by Toko Seimitsu Kogyo Co., Ltd.), a ½ inch (1.25 mm) tip spherical shape The impact piercing strength was measured under the following conditions.

(3) Oxygen barrier properties (oxygen permeability)
The oxygen permeability of the film was measured in accordance with ASTM D3985 in an atmosphere of 23 ° C., a relative humidity of 60% inside the film, and a relative humidity of 50% outside. The measurement used OX-TRAN 10 / 50A made by Modern Controls.
(4) Heat resistance test The obtained film was allowed to stand at 130 ° C for 72 hours in a gear oven (GPHH-200, manufactured by Tabai Co., Ltd.), and then the tensile properties were measured.
(5) Moisture Moisture was calculated from the amount of water volatilized in 30 minutes at a temperature 5 ° C. lower than the melting point of the polyamide under a nitrogen stream using a moisture measuring device (Hiranuma Sangyo Co., Ltd., AQUACOUNTER AQ-2000).

<Example 1>
Polymetaxylylene adipamide (“MX Nylon S6001” manufactured by Mitsubishi Gas Chemical Co., Inc., polyamide resin composed of metaxylylenediamine and adipic acid, relative viscosity = 2.1, moisture 0.03% by mass, terminal amino group concentration 30 [mu] equivalent / g, terminal carboxyl group concentration 75 [mu] equivalent / g, hereinafter may be referred to as "MXD6") 40% by mass, nylon 11 (manufactured by Arkema, Rilsan BESN, hereinafter may be referred to as "N11") 20 mass %, 100% by mass of an amorphous nylon (Novamid X21, glass transition point 125 ° C., manufactured by Mitsubishi Engineering Plastics Co., Ltd., hereinafter sometimes referred to as “X21”) Carbodiimide compound (“Carbodilite LA-1” manufactured by Nisshinbo Industries, Inc., hereinafter referred to as “Carbodilite”) After dry blending with the mass part, the obtained thermoplastic resin composition was set at a speed of 6 kg / hr with a weighing feeder at a speed of 6 kg / hr, set with a torsion type screw having a cylinder diameter of 37 mm and a retention part due to the reverse element. Supplied to a screw extruder. Melt kneading was performed under conditions of a cylinder temperature of 270 ° C. and a screw rotation speed of 100 rpm, and the molten strand was cooled and solidified with cooling air, and then pelletized to produce pellets of a thermoplastic resin composition.
The pellets obtained above were fed to a twin-screw extruder with a T die having a cylinder diameter of 20 mm at a rate of 1.2 kg / hr with a weighing feeder. After melt kneading under the conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 80 rpm, the film-like material is extruded through a T-die and solidified on a cooling roll at 70 ° C. while being drawn at a speed of 2.7 m / min. A 100 μm film was obtained. The evaluation results of the obtained film are shown in Table 1.

<Example 2>
A film was produced in the same manner as in Example 1 except that a thermoplastic resin composition containing 40% by mass of polymetaxylylene adipamide, 30% by mass of nylon 11 and 30% by mass of amorphous nylon was used. It was. The evaluation results of the obtained film are shown in Table 1.

<Comparative Example 1>
A film was produced in the same manner as in Example 1 except that a thermoplastic resin composition containing 55% by mass of polymetaxylylene adipamide and 45% by mass of nylon 11 was used. The evaluation results of the obtained film are shown in Table 1.

<Comparative example 2>
A film was produced in the same manner as in Example 1 except that a thermoplastic resin composition containing 45% by mass of polymetaxylylene adipamide and 55% by mass of nylon 11 was used. The evaluation results of the obtained film are shown in Table 1.

<Comparative Example 3>
A film was prepared in the same manner as in Example 1 except that only nylon 11 was used as the thermoplastic resin composition. The evaluation results of the obtained film are shown in Table 1.

<Comparative example 4>
A film was produced in the same manner as in Example 1 except that only amorphous nylon was used as the thermoplastic resin composition. The evaluation results of the obtained film are shown in Table 1.

As apparent from Table 1 above, in Examples 1 to 4 using polymetaxylylene adipamide, nylon 11, polyamide having a glass transition point of 110 ° C. or higher, and a polycarbodiimide compound, polymetaxylylene adipamide and Compared with Comparative Examples 1 to 4 using a mixture of nylon 11, nylon 11, and a polyamide having a glass transition point of 110 ° C. or higher, a thermoplastic resin composition having excellent barrier properties, mechanical properties, and heat resistance. Obtained.

  The thermoplastic resin composition of the present invention is excellent in barrier properties, strength, impact resistance, and heat resistance, and is suitably used for various molded articles such as fuel containers, tubes, and parts.

Claims (7)

  70% by mole or more of the diamine structural unit is derived from metaxylylenediamine, and 70% by mole or more of the dicarboxylic acid structural unit is derived from an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms (a -1), nylon 11 (a-2), and polyamide (a-3) having a glass transition point of 110 ° C. or higher, wherein (a-1) component is 5 to 60% by mass, and (a-2) component Is a carbodiimide compound (B) having 2 or more carbodiimide groups with respect to 100 parts by mass of the polyamide resin composition (A) having 5 to 60% by mass and 5 to 50% by mass of the component (a-3). A thermoplastic resin composition comprising 1 to 10 parts by mass.   The thermoplastic resin composition according to claim 1, wherein 30 mol% or less of the dicarboxylic acid structural unit of the polyamide resin (a-1) is derived from isophthalic acid.   The thermoplastic resin composition according to claim 1, wherein the moisture content of the polyamide resin composition (A) is 0.3 mass% or less.   The thermoplastic resin composition according to claim 1, wherein the carbodiimide compound (B) is an aliphatic or alicyclic polycarbodiimide compound.   The thermoplastic resin composition according to claim 1, wherein the polyamide (a-3) having a glass transition point of 110 ° C. or higher is amorphous nylon.   The molded object formed using the thermoplastic resin composition in any one of Claims 1-5.   The molded article according to claim 6, which is a multilayer molded article having at least one layer made of the thermoplastic resin composition.