JP5729189B2 - Polyamide resin composition - Google Patents

Description

  The present invention relates to a polyamide resin composition, and in particular, relates to a polyamide resin composition having a high elastic modulus, a low water absorption rate, an excellent barrier property, and an improved flexibility.

Polyamide resins are generally widely used as engineering plastics having excellent mechanical properties, chemical resistance, oil resistance, gas barrier properties, and the like.
Polyamide resin obtained by polymerizing metaxylylenediamine and adipic acid (hereinafter sometimes referred to as “MXD6 polyamide”) has higher strength, higher elastic modulus and lower water absorption than polyamide 6 and polyamide 66, etc. In addition, since it has excellent gas barrier properties, it is widely used because it can be co-extruded or co-injected with a thermoplastic resin such as polyethylene terephthalate, polyamide 6, polyethylene and polypropylene.

  However, although MXD6 polyamide has a high elastic modulus, its elongation is poor, and a film or sheet made of this is too hard and can be used for applications that require rigidity, but for applications that require elongation. Can not be used. In addition, there is a problem that the transparency tends to be lowered due to whitening and crystallization during storage in a high humidity atmosphere or contact with water or boiling water. So far, no polyamide resin having a high elastic modulus and flexibility has been found.

  In the patent document 1, the present applicant has proposed a composition in which MXD6 polyamide is mixed with another specific aliphatic polyamide resin (for example, polyamide 6) having a high crystallization rate. Films and sheets obtained from this polyamide resin composition have excellent characteristics of maintaining excellent transparency even in a high humidity atmosphere, but have the disadvantage of increasing the water absorption rate, and are mixed with other polyamide resins. As a result, there is a problem that the gas barrier property is lowered as compared with the case of MXD6 polyamide alone. Moreover, the flexibility required for applications requiring softness is insufficient.

  On the other hand, a polyamide resin obtained by polycondensation of metaxylylenediamine and sebacic acid (hereinafter sometimes referred to as “MXD10 polyamide”) has been proposed and used in applications such as films because of its good elongation characteristics. There is expected. However, although the film etc. obtained show a certain amount of elongation, they are not sufficient, and further improvements have been demanded for films, sheets, tubes and the like.

Japanese Unexamined Patent Publication No. 4-198329

  An object of the present invention is to provide a polyamide resin composition having a high elastic modulus, a good gas barrier property, a low water absorption, and excellent flexibility, from the above situation.

  As a result of intensive studies to achieve the above object, the present inventors have made a polyether copolymer polyamide comprising a polyamide 12 unit or a polyamide 11 unit and a polyether unit in the xylylenediamine polyamide resin (A). It has been found that by blending a specific amount of (B), a polyamide resin composition suitable for the above purpose can be obtained, and the present invention has been completed.

  That is, according to the first invention of the present invention, a polyamide resin in which 70 mol% or more of the diamine structural unit is derived from xylylenediamine and 50 mol% or more of the dicarboxylic acid structural unit is derived from sebacic acid or adipic acid ( 60 to 99% by mass of A) and 40 to 1% by mass of a polyether copolymerized polyamide (B) composed of polyamide 12 units or polyamide 11 units and polyether units Is provided.

  According to the second invention of the present invention, there is provided a polyamide resin composition characterized in that, in the first invention, xylylenediamine is metaxylylenediamine, paraxylylenediamine or a mixture thereof. Is done.

  According to the third invention of the present invention, in the first or second invention, the carbodiimide compound (C) is further contained in an amount of 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin (A). A polyamide resin composition is provided.

  According to the fourth invention of the present invention, there is provided a polyamide resin composition characterized in that, in the third invention, the carbodiimide compound (C) is an aliphatic or alicyclic polycarbodiimide compound. .

  According to the fifth invention of the present invention, in any one of the first to fourth inventions, the stabilizer (D) is further added in an amount of 0.01 to 1 mass with respect to 100 parts by mass of the polyamide resin (A). The polyamide resin composition characterized by containing a part is provided.

  According to the sixth invention of the present invention, in the fifth invention, the stabilizer (D) is selected from an inorganic stabilizer, an aromatic secondary amine stabilizer and an organic sulfur stabilizer. A polyamide resin composition is provided.

  According to the seventh invention of the present invention, in any one of the first to sixth inventions, the polyamide resin (A) is a polyamide resin obtained by polycondensation of metaxylylenediamine and sebacic acid. A polyamide resin composition is provided.

  According to the eighth invention of the present invention, in any one of the first to sixth inventions, the polyamide resin (A) is a polyamide resin obtained by polycondensation of metaxylylenediamine and adipic acid. A polyamide resin composition is provided.

According to the ninth invention of the present invention, in any one of the first to eighth inventions, the tensile elastic modulus (E) when the film is used is the tensile elasticity when the polyamide resin (A) is used as the film. _A polyamide resin composition characterized by exhibiting an elastic modulus of 70 to 97% with respect to the modulus (E _A ) is provided.

  According to the tenth aspect of the present invention, there is provided a molded article formed by molding the polyamide resin composition according to any one of the first to ninth aspects.

  According to an eleventh aspect of the present invention, there is provided a molded product according to the tenth invention, wherein the molded product is a film, a sheet or a tube.

  Furthermore, according to the twelfth aspect of the present invention, a film made of the polyamide resin composition of any one of the first to ninth aspects and a fiber material (F) are laminated, and the laminate is heated and pressurized. A composite material is provided.

In the present invention, it has been found that the polyamide resin (A) and the polyether copolymer polyamide (B) composed of the polyamide 12 unit or the polyamide 11 unit and the polyether unit are extremely familiar to each other, When these copolymerized polyether copolymerized polyamides (B) are blended in a specific amount ratio of 40 to 1% by mass and polyamide resin (A) in a specific amount ratio of 60 to 99% by mass, surprisingly, while being excellent in elastic modulus, The present inventors have found that a polyamide resin material that exhibits high tensile elongation, is soft, and has excellent gas barrier properties can be achieved.
According to the present invention, a polyamide resin composition having a high elastic modulus, good gas barrier property, low water absorption, and improved flexibility can be obtained.
In particular, a molded product obtained using the polyamide resin composition of the present invention is expected to be used in various applications as a film, a sheet, a tube or the like.
Moreover, since the polyamide resin composition of the present invention provides a polyamide resin material that is excellent in elastic modulus and gas barrier properties, hardly absorbs water, and has improved flexibility, various films, sheets, laminated films, laminated sheets, It can be suitably used for various molded bodies such as various containers such as tubes, hoses, pipes, hollow containers, bottles, and various parts.
For example, a film obtained using the polyamide resin composition of the present invention exhibits a high level of practical physical properties, a tensile elastic modulus of 1000 to 2500 MPa, a tensile elongation of 200 to 500%, and an oxygen permeability coefficient of 0.5 to 3.5 cc. * Mm / m < ² > * day * atm and water absorption 0.1-1.0%.

  The polyamide resin (A) in the polyamide 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), A polyamide resin (A) in which 70 mol% or more of the structural units is derived from xylylenediamine and 50 mol% or more of the dicarboxylic acid structural units is derived from sebacic acid or adipic acid is used.

The polyamide resin (A) is composed of a diamine component containing xylylenediamine at 70 mol% or more, preferably 80 mol% or more, and sebacic acid or adipic acid at 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol%. It is obtained by polycondensation of a dicarboxylic acid component containing at least%.
If the xylylenediamine is less than 70 mol%, the final polyamide resin composition has insufficient barrier properties, and if the sebacic acid or adipic acid is less than 50 mol%, the polyamide resin composition becomes hard. Workability deteriorates.
As the xylylenediamine, it is preferable to use metaxylylenediamine, paraxylylenediamine or a mixture thereof. When mixed and used, it can be used at an arbitrary ratio, but when heat resistance is important, metaxylylenediamine 0 to 50 mol% and paraxylenediamine 50 to 100 mol% are preferable. When emphasizing molding processability, metaxylylenediamine 50 to 100 mol% and paraxylenediamine 0 to 50 mol% are preferable.

As diamines other than xylylenediamine used as a raw material diamine component of the polyamide resin (A), tetramethylenediamine, pentamethylenediamine, 2-methylpentanediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Aliphatic diamines such as decamethylenediamine, dodecamethylenediamine, 2,2,4-trimethyl-hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 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) propane, bis Cycloaliphatic diamines such as aminomethyl) decalin (including structural isomers), bis (aminomethyl) tricyclodecane (including structural isomers), bis (4-aminophenyl) ether, paraphenylenediamine, bis Examples thereof include diamines having an aromatic ring such as (aminomethyl) naphthalene (including structural isomers), and one kind or a mixture of two or more kinds can be used.
When a diamine other than xylylenediamine is used as the diamine component, it is used in a proportion of less than 30 mol%, preferably 1 to 25 mol%, particularly preferably 5 to 20 mol% of the diamine structural unit.

  The sebacic acid or adipic acid used as the raw material dicarboxylic acid component of the polyamide resin (A) is used in an amount of 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. When high elastic modulus is important, adipic acid is preferable, and when flexibility and low water absorption are important, sebacic acid is preferable. Further, the more the sebacic acid component is, the better the compatibility with the polyether copolymerized polyamide (B) is, and the haze tends to be lowered.

  As a raw material dicarboxylic acid component other than sebacic acid and adipic acid, α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms other than sebacic acid and adipic acid can be preferably used. For example, succinic acid, glutaric acid, Examples thereof include aliphatic dicarboxylic acids such as pimelic acid, suberic acid, azelaic acid, undecanedioic acid, and dodecanedioic acid, which can be used alone or in combination.

As dicarboxylic acid components other than sebacic acid and adipic acid, aromatic dicarboxylic acid can also be used, phthalic acid compounds such as isophthalic acid, terephthalic acid, 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-naphthalenedicarboxylic acid, 2 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and the like isomers such as naphthalenedicarboxylic acid are exemplified, and one or two or more kinds can be mixed and used.
Also, monocarboxylic acids such as benzoic acid, propionic acid and butyric acid, polycarboxylic acids such as trimellitic acid and pyromellitic acid, carboxylic acid anhydrides such as trimellitic anhydride and pyromellitic anhydride may be used in combination. it can.
When a dicarboxylic acid other than an α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component other than sebacic acid and adipic acid, isophthalic acid is used from the viewpoint of molding processability and barrier properties. Is preferably used. The proportion of isophthalic acid is less than 30 mol%, preferably 1 to 25 mol%, particularly preferably 5 to 20 mol% of the dicarboxylic acid structural unit.

The polyamide resin (A) is obtained by polycondensation of a diamine component containing 70 mol% or more of xylylenediamine and a dicarboxylic acid component containing 50 mol% or more of sebacic acid or adipic acid. A method is not specifically limited, It manufactures by conventionally well-known methods and polymerization conditions, such as a normal pressure melt polymerization method and a pressure melt polymerization method.
For example, it is produced by a method in which a polyamide salt composed of metaxylylenediamine and sebacic acid (or adipic acid) is heated in the presence of water under pressure, and polymerized in a molten state while removing added water and condensed water. The It can also be produced by a method in which metaxylylenediamine is directly added to molten sebacic acid (or adipic 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 temperature of 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) 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 as long as the performance is not impaired.

The polyamide resin (A) 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. After that, after heating and crystallizing using a grooved stirring and heating method, a method of further heat treatment, using a hopper-shaped heating device, the heat treatment is performed in an inert gas atmosphere. And a method of performing a heat treatment using a batch heating device such as a rotating drum after crystallization using a groove type stirring and heating device.
Among these, a method of performing crystallization and heat treatment using a batch heating apparatus is preferable. As conditions for the crystallization treatment, the temperature is raised to 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. Crystallized, and then in an inert gas atmosphere or under reduced pressure, at a temperature of [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) is preferably controlled in the range of 150 ° C. to 310 ° C., more preferably 160 to 300 ° C., further preferably 170 to 290 ° C. By making the melting point in the above range, the processability tends to be improved, which is preferable.
Moreover, it is preferable that the glass transition point of a polyamide resin (A) is the range of 50-130 degreeC. By making the glass transition point in the above range, the gas barrier property tends to be good, which is preferable.

  In the present invention, the melting point and glass transition point of the polyamide resin (A) and the later-described polyether copolymerized polyamide (B) can be measured by a differential scanning calorimetry (DSC) method. The melting point and the glass transition point measured by raising the temperature again after eliminating the influence of the thermal history on the crystallinity. Specifically, for example, the temperature is raised at a rate of 10 ° C./min from 30 ° C. to a temperature higher than the expected melting point, held for 2 minutes, and then lowered to 30 ° C. at a rate of 20 ° C./min. Next, the temperature is raised to a temperature higher than the melting point at a rate of 10 ° C./min, and the melting point and glass transition point can be determined.

  The polyamide resin (A) preferably has a terminal amino group concentration of less than 100 μeq / g, more preferably 5 to 75 μeq / g, still more preferably 10 to 50 μeq / g, and a terminal carboxyl group concentration of preferably less than 100 μeq / g. Preferably, 10 to 90 μeq / g, more preferably 10 to 50 μeq / g is preferably used. By setting the terminal amino group concentration and the terminal carboxyl group concentration within the above ranges, the reaction with the carbodiimide compound (C) described later becomes easy, and the hydrolysis resistance tends to be good.

The polyamide resin (A) preferably has a relative viscosity of 1.7 to 4 measured in 96% sulfuric acid at a resin concentration of 1 g / 100 cc and a temperature of 25 ° C., more preferably 1.9 to 3.8. preferable.
The number average molecular weight of the polyamide resin (A) is preferably 6,000 to 50,000, and more preferably 10,000 to 43,000. Within the above range, the mechanical strength and moldability tend to be good.

The polyamide resin (A) may contain a phosphorus compound in order to increase the 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, and examples thereof include phosphates such as sodium, magnesium, and calcium, hypophosphites, and phosphites. Among these, it is preferable to contain a hypophosphite of an alkali metal or an alkaline earth metal because the anti-coloring effect of the polyamide resin is particularly excellent. When a phosphorus compound is used, the polyamide resin is used so that the phosphorus atom concentration in the finally obtained polyamide resin composition is 1 ppm to 200 ppm, preferably 5 ppm to 160 ppm, more preferably 10 ppm to 100 ppm. It is desirable to contain in A).
In addition to the above phosphorus compound, the polyamide resin (A) includes a lubricant, a matting agent, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a nucleating agent, a plasticizer, and the like within a range not impairing the effects of the present invention. Additives such as additives, flame retardants, antistatic agents, anti-coloring agents, anti-gelling agents, etc. can be added, but not limited to those shown above, various materials can be mixed and added Also good.

In the present invention, a polyamide copolymer (B) composed of polyamide 12 units or polyamide 11 units and polyether units is blended with the polyamide resin (A).
Polyether copolymer polyamide (B) composed of polyamide 12 units or polyamide 11 units and polyether units is composed of polyamide 12 units (dodecanamide units) or polyamide 11 units (undecanamide units) and polyoxyalkylene glycols and the like. Mainly composed of ether units. Usually, it is mainly composed of 15 to 90% by mass of polyamide units containing 12 units of polyamide or 11 units of polyamide and 85 to 10% by mass of polyether units. The polyether copolymerized polyamide (B) used in the present invention is preferably a segmented copolymer.

  As the polyether unit constituting the polyether copolymerized polyamide (B), a polyoxyalkylene oxide unit is preferable. The polyalkylene oxide unit is preferably composed of oxyalkylene units having 2 to 4 carbon atoms and having a molecular weight of 200 to 8,000, specifically, polyethylene oxide, polypropylene oxide, polybutylene oxide units (or glycols thereof). Unit of origin) and the like.

  The number average molecular weight of the polyether copolymerized polyamide (B) is preferably 15,000 to 35,000. By setting the number average molecular weight within the above range, the dispersibility in the polyamide resin (A) becomes good, and the hydrolysis resistance and flexibility tend to be improved. The relative viscosity measured in 96% sulfuric acid at a resin concentration of 1 g / 100 cc and a temperature of 25 ° C. is preferably 1.5 to 4.5, more preferably 1.6 to 4.2. It is more preferable to use 8-4.

The polyether copolymerized polyamide (B) has a melting point or softening point of preferably 175 ° C. or lower, more preferably 170 ° C. or lower. By using such a polyether copolymerized polyamide (B), there is an advantage that the dispersibility in the polyamide resin (A) is further improved.
The softening point is a temperature measured in accordance with JIS K2207 standard.

  The above-mentioned polyether copolymerized polyamide (B) preferably has a terminal amino group concentration of 1 to 100 μeq / g, more preferably 2 to 50 μeq / g, and a terminal carboxyl group concentration of preferably 1 to 100 μeq. / G, more preferably 2 to 50 μeq / g is preferably used. By setting the terminal amino group concentration and the terminal carboxyl group concentration within the above ranges, the reaction with the carbodiimide compound described later is facilitated and the hydrolysis resistance tends to be good.

The polyether copolymerized polyamide (B) can be produced by a known method, for example, a polyamide 11 forming component such as undecane lactam or 11-aminoundecanoic acid, or a polyamide 12 forming property such as dodecane lactam or 12-aminododecanoic acid. A polyamide segment is formed from the components and other polyamide-forming components, and a polyether segment is added thereto, followed by polymerization at a high temperature and under reduced pressure.
Moreover, the polyether copolymerized polyamide (B) is commercially available, and may be appropriately selected from these.

  The polyamide resin composition of the present invention contains 1 to 40% by mass of the polyether copolymerized polyamide (B) when the total of the polyamide resin (A) and the polyether copolymerized polyamide (B) is 100% by mass. Within such a range, the flexibility of the polyamide resin composition is improved and the water absorption can be lowered. The preferable content of the polyether copolymerized polyamide (B) is 5 to 40% by mass, and the more preferable content is 5 to 35% by mass, and particularly preferably 10 to 30% by mass.

  It is preferable to mix | blend the carbodiimide compound (C) with the polyamide resin composition of this invention. Preferred examples of the carbodiimide compound (C) include aromatic, aliphatic or alicyclic polycarbodiimide compounds produced by various methods. Among these, an aliphatic or alicyclic polycarbodiimide compound is preferable, and an alicyclic polycarbodiimide compound is more preferably used from the viewpoint of melt kneading properties during extrusion and the like.

  These carbodiimide compounds (C) 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. . The isocyanate group content is preferably 0.1 to 5% by mass, more preferably 1 to 3% by mass. By setting it as the above ranges, the reaction with the polyamide resin (A) and the polyether copolymerized polyamide (B) is facilitated, and the hydrolysis resistance tends to be good.

As organic polyisocyanate which is a synthesis raw material of the carbodiimide compound (C), 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-dii Cyanate, methylenebis (4,1-cyclohexylene) = can be exemplified diisocyanate may be used in combination of two or more thereof. Among these, dicyclohexylmethane-4,4-diisocyanate and methylenebis (4,1-cyclohexylene) = diisocyanate are preferable.

  It is also preferable to use an end-capping agent such as monoisocyanate in order to seal the end of the carbodiimide compound (C) and control the degree of polymerization. Examples of the monoisocyanate include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate, and two or more kinds may be used in combination.

  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 such as methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, polyethylene glycol monomethyl ether, and polypropylene glycol monomethyl ether. -OH group compounds, secondary amines such as diethylamine and dicyclohexylamine, primary amines such as butylamine and cyclohexylamine, carboxylic acids such as succinic acid, benzoic acid and cyclohexanecarboxylic acid, ethyl mercaptan, allyl mercaptan, thiophenol, etc. Examples of these compounds include thiols and compounds having an epoxy group, and two or more of them may be used in combination.

  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 methyl-2-phospholene-1-oxide and phospholene oxides such as these 3-phospholene isomers, tetrabutyl titanate, etc. can be used. -Methyl-1-phenyl-2-phospholene-1-oxide is preferred. Two or more carbodiimidization catalysts may be used in combination.

  The preferable content of the carbodiimide compound (C) is 0.1 to 2 parts by mass, more preferably 0.2 to 1.5 parts by mass, and still more preferably 0 to 100 parts by mass of the polyamide resin (A). .3 to 1.5 parts by mass. If the amount is less than 0.1 parts by mass, the resin composition does not have sufficient hydrolysis resistance, uneven discharge during melt kneading such as extrusion tends to occur, and melt kneading tends to be insufficient. On the other hand, when it exceeds 2 parts by mass, the viscosity of the resin composition during melt kneading is remarkably increased, and melt kneadability and moldability are liable to deteriorate.

  Moreover, it is preferable to mix | blend a stabilizer (D) with the polyamide resin composition of this invention. Examples of the stabilizer include, for example, phosphorus-based, hindered phenol-based, hindered amine-based, organic sulfur-based, oxalic acid anilide-based, aromatic secondary amine-based organic stabilizers, copper-based compounds, halide-based inorganic systems, and the like. Stabilizers are preferred. As a phosphorus stabilizer, a phosphite compound and a phosphonite compound are preferable.

  Examples of the phosphite compound include distearyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and bis (2,6- Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t- Butyl-4-isopropylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-sec-) Butylphenyl) pentaerythritol diphosphite, bis (2,6-di-) -Butyl-4-t-octylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like, and in particular, bis (2,6-di-t-butyl- 4-methylphenyl) pentaerythritol diphosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferred.

  Examples of the phosphonite compound include tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,5-di-t-butylphenyl) -4,4′-. Biphenylene diphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,3-dimethyl-5-ethylphenyl) -4,4'-biphenylene diphosphonite Tetrakis (2,6-di-t-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3,4-tributylphenyl) -4,4'-biphenylenediphosphonite , Tetrakis (2,4,6-tri-t-butylphenyl) -4,4′-biphenylenediphosphonite, etc. Tetrakis (2,4-di -t- butyl-phenyl) -4,4'-biphenylene phosphonite are preferred.

  Examples of the hindered phenol stabilizer include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1- Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol -Bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,5-di-tert-butyl-4-hydro Cybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, N, N'-hexamethylenebis (3 , 5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Among these, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-t-butyl-4 -Hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-dimethyl-2- {β- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N′-hexamethylenebis (3 5-di-t-butyl-4-hydroxy-hydrocinnamide) is preferred.

  Examples of the hindered amine stabilizer include known hindered amine compounds having a 2,2,6,6-tetramethylpiperidine skeleton. Specific examples of hindered amine compounds include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2 , 6,6-tetramethylpiperidine, 4-phenylacetoxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2 , 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2, 2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-ethylcarba Yloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexylcarbamoyloxy-2,2,6,6-tetramethylpiperidine, 4-phenylcarbamoyloxy-2,2,6,6-tetramethylpiperidine, Bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis (2,2,6,6-tetramethyl) -4-piperidyl) malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) adipate, bis (2,2 , 6,6-tetramethyl-4-piperidyl) terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) eta , Α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl-4-piperidyltolylene) -2 , 4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylene-1,6-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -Benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxylate, 1- [2- {3 -(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] 2,2 , 6,6-tetramethyl Piperidine, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β ′,-tetramethyl-3,9- [ 2,4,8,10-tetraoxaspiro (5,5) undecane] condensate with diethanol, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6, -succinate Examples include polycondensates of tetramethylpiperidine, 1,3-benzenedicarboxamide-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) and the like.

  As a product of a hindered amine compound, products manufactured by ADEKA “ADK STAB LA-52, LA-57, LA-62, LA-67, LA-63P, LA-68LD, LA-77, LA-82, LA-87” "Products manufactured by Ciba Specialty Chemicals Co., Ltd." Tinuvin 622, 944, 119, 770, 144 "; Products manufactured by Sumitomo Chemical Co., Ltd." Sumisorb 577 "; Products manufactured by Cyamide Co., Ltd." Thiasoap UV-3346, 3529, 3853 " And “Nairostav S-EED” manufactured by Clariant Japan.

  Examples of the organic sulfur stabilizer include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate), and thiobis (N-phenyl). -Β-naphthylamine) and other organic thioacid compounds, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, and mercaptobenzimidazole compounds such as metal salts of 2-mercaptobenzimidazole, diethyldithiocarbamine Dithiocarbamate compounds such as metal salts of acids and metal salts of dibutyldithiocarbamate, and thioureas such as 1,3-bis (dimethylaminopropyl) -2-thiourea and tributylthiourea Compounds, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate include trilauryl trithiophosphite and the like.

Among these, mercaptobenzimidazole compounds, dithiocarbamic acid compounds, thiourea compounds, and organic thioacid compounds are preferable, and mercaptobenzimidazole compounds and organic thioacid compounds are more preferable. In particular, a thioether-based compound having a thioether structure can be suitably used because it receives oxygen from an oxidized substance and reduces it. Specifically, 2-mercaptobenzimidazole, 2-mercaptomethylbenzimidazole, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate) are more preferable. Tetradecylthiodipropionate, pentaerythritol tetrakis (3-dodecylthiopropionate) and 2-mercaptomethylbenzimidazole are more preferred, and pentaerythritol tetrakis (3-dodecylthiopropionate) is particularly preferred.
The molecular weight of the organic sulfur compound is usually 200 or more, preferably 500 or more, and the upper limit is usually 3,000.

  As the oxalic anilide stabilizer, 4,4′-dioctyloxyoxanilide, 2,2′-diethoxyoxanilide, 2,2′-dioctyloxy-5,5′-di- Tributoxanilide, 2,2′-didodecyloxy-5,5′-di-tert-butoxanilide, 2-ethoxy-2′-ethyloxanilide, N, N′-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2′-ethoxanilide and its mixture with 2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide, o- and p-methoxy-disubstituted oxanilides Mixtures, o- and p-ethoxy-disubstituted oxanilide mixtures, and the like.

  The aromatic secondary amine type stabilizers, compounds having a diphenylamine skeleton, compounds having compound and dinaphthylamine skeleton having a phenylnaphthylamine skeleton are preferred, compounds having a diphenylamine skeleton, and compounds having a phenylnaphthylamine skeleton is more preferable . Specifically, p, p′-dialkyldiphenylamine (the alkyl group has 8 to 14 carbon atoms), octylated diphenylamine, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, p- (p-toluene) Sulfonylamido) diphenylamine, N, N′-diphenyl-p-phenylenediamine, N-phenyl-N′-isopropyl-p-phenylenediamine, N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylene Compounds having a diphenylamine skeleton such as diamine and N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-1-naphthylamine and N, N′-di-2- Compounds having a phenylnaphthylamine skeleton such as naphthyl-p-phenylenediamine And compounds having a dinaphthylamine skeleton such as 2,2'-dinaphthylamine, 1,2'-dinaphthylamine, and 1,1'-dinaphthylamine. Among these, 4,4′-bis (α, α-dimethylbenzyl) diphenylamine, N, N′-di-2-naphthyl-p-phenylenediamine and N, N′-diphenyl-p-phenylenediamine are more preferable, N, N′-di-2-naphthyl-p-phenylenediamine and 4,4′-bis (α, α-dimethylbenzyl) diphenylamine are particularly preferred.

  When blending the above organic sulfur stabilizer or aromatic secondary amine stabilizer, it is preferable to use them together. By using these in combination, the heat aging resistance of the polyamide resin composition tends to be better than when used alone.

  As a more suitable combination of the organic sulfur stabilizer and the aromatic secondary amine stabilizer, ditetradecylthiodipropionate, 2-mercaptomethylbenzimidazole, and pentaerythritol may be used as the organic sulfur stabilizer. At least one selected from tetrakis (3-dodecylthiopropionate) and an aromatic secondary amine stabilizer are 4,4′-bis (α, α-dimethylbenzyl) diphenylamine and N, N′— Examples thereof include a combination with at least one selected from di-2-naphthyl-p-phenylenediamine. Furthermore, the organic sulfur stabilizer is pentaerythritol tetrakis (3-dodecylthiopropionate), and the aromatic secondary amine stabilizer is N, N′-di-2-naphthyl-p-phenylenediamine. Is more preferable.

  When the organic sulfur stabilizer and the aromatic secondary amine stabilizer are used in combination, the content ratio (mass ratio) in the polyamide resin composition is such that the aromatic secondary amine stabilizer / The organic sulfur stabilizer is preferably 0.05 to 15, more preferably 0.1 to 5, and further preferably 0.2 to 2. By setting it as such content ratio, heat aging resistance can be improved efficiently, maintaining gas barrier property.

As the inorganic stabilizer, a copper compound and a halide are preferable.
The copper compound is a copper salt of various inorganic acids or organic acids, and excludes halides described later. The copper may be either cuprous or cupric. Specific examples of the copper salt include copper chloride, copper bromide, copper iodide, copper phosphate, copper stearate, hydrotalcite, and styhite. And natural minerals such as pyrolite.

  Examples of the halide used as the inorganic stabilizer include, for example, alkali metal or alkaline earth metal halides; ammonium halides and quaternary ammonium halides of organic compounds; alkyl halides, allyl halides. Specific examples thereof include ammonium iodide, stearyltriethylammonium bromide, benzyltriethylammonium iodide, and the like. Among these, alkali metal halide salts such as potassium chloride, sodium chloride, potassium bromide, potassium iodide, sodium iodide and the like are preferable.

  The combined use of a copper compound and a halide, in particular, the combined use of a copper compound and a halogenated alkali metal salt is preferable because it exhibits excellent effects in terms of heat discoloration resistance and weather resistance (light resistance). For example, when a copper compound is used alone, the molded product may be colored reddish brown by copper, and this coloring is not preferable depending on the application. In this case, discoloration to reddish brown can be prevented by using a copper compound and a halide together.

  In the present invention, among the above stabilizers, in particular, from the viewpoint of processing stability at the time of melt molding, heat aging resistance, appearance of molded products, and prevention of coloring, organic sulfur, aromatic secondary amine, and inorganic The stabilizers are particularly preferred.

  Content of the said stabilizer (D) is 0.01-1 mass part normally with respect to 100 mass parts of polyamide resins (A), Preferably it is 0.01-0.8 mass part. By setting the content to 0.01 parts by mass or more, the effect of improving thermal discoloration and weather resistance / light resistance can be sufficiently exerted. By setting the content to 1 part by mass or less, the mechanical properties are lowered. Can be suppressed.

  The polyamide resin composition of the present invention may be blended with other resins other than the polyamide resin (A) and the polyether copolymerized polyamide (B) within a range not impairing the effects of the present invention. Other resins are preferably resins having a functional group that reacts with a carbodiimide group. Specifically, for example, polyamide resin (A), polyamide resin other than polyether copolymerized polyamide (B), polyester resin, polycarbonate resin, polyimide resin, polyurethane resin, acrylic resin, polyacrylonitrile, ionomer, ethylene-acetic acid Examples thereof include vinyl copolymers, fluororesins, vinyl alcohol copolymers such as ethylene-vinyl alcohol, biodegradable resins, and the like, and these can be used alone or in combination.

  In addition, the polyamide resin composition of the present invention includes an inorganic filler, a crystal nucleating agent, a conductive agent, a lubricant, a plasticizer, a releasability improver, a pigment, and a dye as long as the purpose of the present invention is not impaired. , Dispersants, antistatic agents, UV absorbers, impact resistance improvers, flame retardants, and other well-known additives.

  Among them, it is also preferable to blend an inorganic filler, glass-based filler (glass fiber, crushed glass fiber (milled fiber), glass flake, glass beads, etc.), calcium silicate-based filler (wollastonite, etc.), Examples include mica, talc, kaolin, potassium titanate whisker, boron nitride, carbon fiber, etc., and two or more of these may be used in combination.

  It is also preferable to add a nucleating agent in order to increase the crystallization rate and improve the moldability. Examples of the nucleating agent include inorganic nucleating agents such as talc and boron nitride, but an organic nucleating agent may be added. A preferable blending amount of the nucleating agent is 0.01 to 6 parts by mass, more preferably 0.03 to 1 part by mass, in the case of an organic nucleating agent or boron nitride, with respect to 100 parts by mass of the polyamide resin (A). When using another nucleating agent, it is 0.5-8 mass parts, More preferably, it is 1-4 mass parts.

In the polyamide resin composition of the present invention, preferably, the tensile elastic modulus (E) when formed into a film is 70 to 97% relative to the tensile elastic modulus (E _A ) when the polyamide resin (A) is formed into a film. The elastic modulus is shown. When the tensile modulus (E) is 70 to 97% of the tensile modulus (E _A ) of the polyamide resin (A), 1 to 40% by mass of the polyether copolymerized polyamide (B) is blended. However, the decrease in the elastic modulus exceeds 3% and is less than 30%, which means that the elasticity is excellent without being greatly decreased and the elasticity is maintained to some extent. By having such an elastic modulus, a resin composition having a high elastic modulus and excellent flexibility can be provided.
The elastic modulus of the polyamide resin composition and the polyamide resin (A) here is to determine the tensile elastic modulus (MPa) by testing the tensile properties of a film having a thickness of 100 μm according to JIS K7127 and K7161. Is measured.
A specific apparatus uses a strograph manufactured by Toyo Seiki Co., Ltd., the test piece width is 10 mm, the chuck-to-chuck distance is 50 mm, the tensile speed is 50 mm / min, the measurement temperature is 23 ° C., and the measurement humidity is 50% RH. It was measured. The film has a thickness of 100 μm and is an unstretched film.

The method for producing the polyamide resin composition of the present invention is not particularly limited, and the polyamide resin (A) and the polyether copolymerized polyamide (B), and if necessary, the carbodiimide compound (C), the stabilizer (D) and Other components can be produced by mixing in any order to make a dry blend. It can also be produced by further kneading the dry blend. Of these, a melt kneading method using various commonly used extruders such as a single screw or twin screw extruder is preferable, and a method using a twin screw extruder is particularly preferable from the viewpoint of productivity and versatility. At that time, the melt kneading temperature is preferably adjusted to 200 to 300 ° C., and the residence time is preferably adjusted to 10 minutes or less, and the screw has at least one reverse screw element and / or kneading disk, It is preferable to melt and knead while partly staying. By setting the melt-kneading temperature within the above range, it tends to be difficult for extrusion-kneading failure and resin decomposition to occur.
Alternatively, a master resin can be produced by melt-kneading a polyamide resin additive at a high concentration in advance, and then diluted with a polyamide resin to produce a composition having a predetermined blending ratio.

The polyamide resin composition of the present invention can be molded into various films, sheets, laminated films, laminated sheets, tubes, hoses, pipes, hollow containers, various containers such as bottles, various parts and the like by a conventionally known molding method. Can be molded into a body.
Typical film-forming methods for producing a film or sheet include a T-die method in which a film or sheet extruded from a T-type die is cooled and solidified by casting with a chilled roll, and a die-to-tube having an annular slit. For example, an inflation method may be used in which a shaped product is extruded and air is blown into a tube to be expanded and air-cooled or water-cooled to be molded. The film / sheet thus formed is used as a stretched film / sheet as it is unstretched or through a stretching process such as uniaxial stretching or biaxial stretching.
Moreover, a single layer may be sufficient and lamination | stacking with other resin by coextrusion, a lamination, etc. may be sufficient.

  The thickness of the film / sheet is not particularly defined, but the thickness of the polyamide resin monolayer is preferably 1 to 200 μm, more preferably 2 to 100 μm, when unstretched. Most preferably, it is 10-50 micrometers. In the stretched film / sheet, the thickness is preferably 2 to 50 μm. When laminated, the thickness of the laminated film / sheet as a whole is preferably 10 to 3000 μm, and the thickness of the polyamide resin layer is preferably in the same range as the thickness of the single layer.

  The method for producing the polyamide tube is not particularly limited, and can be produced by employing a known technique. For example, the dry blend or melt-kneaded pellets may be supplied to a tube extruder and molded according to a conventional method. There are no particular restrictions on the molding conditions, and a normal polyamide resin molding temperature can be employed. The wall thickness of the tube is preferably 0.1 to 2 mm. If the wall thickness is less than 0.1 mm, the shape of the tube may not be maintained. On the other hand, if the wall thickness exceeds 2 mm, the tube will become hard and the flexibility of the tube will decrease, making it difficult to assemble the product. Absent

  The polyamide resin composition of the present invention can also provide a layer excellent in hydrolysis resistance, barrier properties, flexibility, strength, and impact resistance in a single layer or laminated. In the case of a multilayer, particularly from the viewpoint of the strength of the molded article, it contains at least one layer comprising the polyamide resin composition of the present invention, and other than polyolefin resin, polystyrene resin, polyester resin, polycarbonate resin or the polyamide resin composition of the present invention. A multilayer molded body in which at least one reinforcing layer made of a polyamide resin, a fluorine-based resin or the like is laminated is preferable.

  The polyolefin resin used for the reinforcing layer is 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. The copolymer of the above olefin and those mixtures can be illustrated. In addition, the polyolefin resin, polystyrene resin, polyester resin, polycarbonate resin, and polyamide resin other than the polyamide resin composition of the present invention exemplified in the reinforcing layer may be used in combination with each other, such as an elastomer. It can also be used by mixing with other resins and additives such as carbon black and flame retardant.

It is also preferable to laminate a polyamide resin composition film with the fiber material (F) and heat and press the resulting laminate to obtain a polyamide / fiber material composite.
In order to obtain such a composite material, it is preferable to use a film that is as thin as possible. In order to make the polyamide resin composition into a thin film of, for example, 50 μm or less, it may be formed directly. Alternatively, the polyamide resin composition and the polyolefin resin are laminated to obtain a laminated film, from which the polyolefin resin layer is peeled off. It is also preferable to manufacture it.
There is no restriction | limiting in particular about the method of manufacturing a laminated resin film, A well-known method is employable. A preferred method will be described. A polyamide resin composition and a polyolefin resin are co-extruded using, for example, a T-die co-extruder, an inflation co-extruder, etc. obtain.

The laminated resin film may have a two-layer structure of polyolefin resin layer / polyamide resin composition layer or a three-layer structure of polyolefin resin layer / polyamide resin composition layer / polyolefin resin layer.
In the case of manufacturing by T-die coextrusion, each molten resin kneaded and extruded by an extruder is introduced into a T-die that can be laminated in two or two layers or two or three layers, laminated inside, and a molten film And extruded from a T die. Here, the layer ratio of each layer can be set as various layer ratios, and the extruded molten film is pressure-cooled by a cooling roll and formed into a predetermined film thickness.
As a film thickness of a laminated film, it is preferable that a polyamide resin composition layer is 5-50 micrometers, More preferably, it is 10-30 micrometers. Within this range, the moldability of the laminated film is good.
Moreover, it is preferable that the thickness of a polyolefin resin layer is about 5-50 micrometers, More preferably, it is 10-30 micrometers. It is preferable for the thickness of the polyolefin resin layer to be in the above range because the moldability of the laminated resin film tends to be good. Further, when peeling the laminated film, the peelability between layers is good, the take-up property of the polyamide resin composition layer is good, and it tends to be a film roll made of a polyamide resin composition without winding wrinkles, which is preferable. .

The polyolefin resin used for lamination is a resin represented by a polyethylene resin or a polypropylene resin.
Specific examples of the polyethylene resin include low density polyethylene (LDPE), high density polyethylene (HDPE), medium density polyethylene (MDPE), high pressure method low density polyethylene (HPLDPE), linear low density polyethylene (LLDPE), super Low density polyethylene (VLDPE), low crystalline ethylene-1-butene random copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer Examples include coalescence. These may be used alone or in combination of two or more.

  As the polyolefin resin, polypropylene, high-pressure method low-density polyethylene (HPLDPE), and linear low-density polyethylene (LLDPE) are preferable. Particularly, high-pressure method low-density polyethylene (HPLDPE) is stable in moldability and peelable. It is effective from the point of view.

The polyolefin resin has sufficient release performance from the polyamide resin composition, but may contain a release agent if necessary. As the release agent, known glyceride release agents and the like can be used. Content in the case of mix | blending a peeling agent is 0.1-10 mass parts with respect to 100 weight part of polyolefin resin, Preferably it is 1-5 mass parts.
The polyolefin resin may contain a slip agent. By containing a slip agent, it becomes easy to wind up a two-layer film of polyolefin resin layer / polyamide resin composition layer or a three-layer laminated film of polyolefin resin layer / polyamide resin composition layer / polyolefin resin layer. The laminated film roll having excellent quality can be obtained, and the polyamide resin composition film from which the roll has been peeled tends to be free of wrinkles.

For the polyamide resin composition film, the polyolefin resin layer is peeled off from the two-layer film of the polyolefin resin layer / polyamide resin composition layer or the three-layer laminated film of the polyolefin resin layer / polyamide resin composition layer / polyolefin resin layer. Can be manufactured. Through such a process, a thin film film of a polyamide resin composition can be obtained. The polyolefin resin layer may be peeled by any method. Industrially, the polyolefin resin layer is peeled off by a peeling roll or the like, and the obtained polyamide resin composition film is wound up.
The film thickness of the obtained polyamide resin composition film is preferably thin, preferably 5 to 50 μm, and more preferably 10 to 30 μm.

  As mentioned above, although the method to manufacture a film via a laminated film was demonstrated, it can also be made into a film directly, for example, a polyamide resin composition can be extruded by a single layer and processed into a film form. In this case, it is also preferable to employ a method of applying a texture to the film surface to form the film. In particular, it is effective in the case where it is easy to break when trying to process thinly due to the application of minute stress or uneven stress during molding. When the film is formed with a textured surface, that is, a film having a textured surface with fine irregularities on the surface, the frictional resistance between the film surface and the take-up machine, i.e. It is considered that the film can be prevented from being broken because the stress applied to the film is reduced and can be controlled uniformly. Moreover, when winding up in roll shape, it is possible to reduce friction between film surfaces and to wind up without a wrinkle, to relieve | moderate the stress at the time of winding, and to prevent the fracture | rupture of a film. Furthermore, when slitting a film roll to an arbitrary width or after processing such as pasting with another film by dry lamination, it prevents friction with the device and prevents breakage, thus improving productivity. it can.

The film made of the polyamide resin composition produced by such a method is laminated with the fiber material (F).
Examples of the fiber material (F) include plant fibers, carbon fibers, glass fibers, alumina fibers, boron fibers, ceramic fibers, aramid fibers, polyoxymethylene fibers, aromatic polyamide fibers, polyparaphenylene benzobisoxazole fibers, steel fibers, etc. Metal fibers and the like. Among these, carbon fibers are preferably used because they have excellent characteristics of high strength and high elastic modulus while being lightweight.

These fiber materials can be in various forms such as, for example, those arranged in only one direction, a fabric such as a knitted fabric, a nonwoven fabric, or a mat. Among these, the form of a fabric, a nonwoven fabric or a mat is preferable. Furthermore, a prepreg in which these are laminated, shaped, and impregnated with a binder or the like is also preferably used.
In addition, in order to improve wettability and interfacial adhesion with the polyamide resin composition, a silane coupling agent, a sizing agent or a surface treatment agent (for example, an epoxy compound, an acrylic compound, an isocyanate compound, a silane compound, It is also preferable to use those surface-treated with a functional compound such as a titanate compound).

The fiber length of the fiber material (F) is determined when the step of laminating the polyamide resin composition film and the fiber material (F) takes a step of applying pressure after the fiber material (F) is sprinkled on the polyamide resin composition film. 3 to 100 mm is preferable, and 5 to 50 mm is more preferable. Moreover, the diameter of a fiber is 5-30 micrometers from the point which ensures the reinforcement effect, More preferably, it is 7-25 micrometers.
When the step of laminating the polyamide resin composition film and the fiber material (F) takes the step of pressurizing the fiber material (F) wound around the polyamide resin composition film and the bobbin, or when wound around the bobbin In the case of taking the step of pressing while feeding the monofilament fiber material (F), the diameter of the fiber material (F) is preferably 1 to 300 μm, more preferably 2 to 200 μm, and further preferably 3 to 100 μm. Within this range, the resulting composite material tends to have good strength.

Such a fiber material (F) is laminated | stacked with the film of the above-mentioned polyamide resin composition, and is set as a laminated body. Lamination can be performed by a known method, for example, by feeding a polyamide resin film on a roll while feeding the fiber material and laminating with a pressure roll.
As for the thickness of the obtained laminate, the fiber material (F) layer is preferably 5 to 300 μm, more preferably about 10 to 250 μm, and the polyamide resin composition layer is preferably 5 to 50 μm, more preferably 7 to 30 μm. Yes, particularly preferably 10 to 25 μm.

By heating and pressurizing the obtained laminate, the whole amount or at least a part of the polyamide resin composition is melted, impregnated in the fiber material (F) layer, and consolidated (densified).
It is preferable that the heating and pressurization is performed on a superposed product obtained by superimposing a plurality of laminates of polyamide resin composition film / fiber material. For example, it is desirable to heat and press at least two sheets, preferably five or more of the polyamide resin composition film / fiber material laminate, with respect to the superposed product so that both outer sides thereof become polyamide resin layers.

  In the heating and pressurization, the temperature for the impregnation of the polyamide resin composition into the fiber material layer and the integration thereof must be equal to or higher than the temperature at which the polyamide resin (A) is softened and melted. Generally, a temperature range from a glass transition point + 10 ° C. or higher to a thermal decomposition temperature −20 ° C. is preferable although it varies depending on the type and molecular weight. Moreover, melting | fusing point +10 degreeC or more is preferable, More preferably, it is melting | fusing point +20 degreeC or more. By heating and pressurizing in such a temperature range, the fiber material (F) is better impregnated with the polyamide resin composition, and the physical properties of the molded product are improved. Further, the pressing pressure for molding is preferably 1 MPa or more, more preferably 5 MPa or more, and particularly preferably 10 MPa or more. The heating and pressurization is preferably performed under reduced pressure, particularly under vacuum. When performed under such conditions, it is preferable that bubbles do not easily remain.

The composite material thus obtained is preferably further heat-treated. By heat-treating the composite material, the low warpage and dimensional stability of the molded product can be further improved. The heat treatment temperature is preferably 120 to 180 ° C, more preferably 140 to 170 ° C, and further preferably 150 to 160 ° C. Within this range, the crystallization of the polyamide resin (A) proceeds rapidly, and the low warpage and dimensional stability of the molded product can be further improved.
The heat treatment can be performed after the composite material is taken out of the mold, or can be performed in the mold. When performing in a mold, it may be processed in a mold different from the mold formed with the composite material, or the same mold temperature can be changed to a temperature suitable for heat treatment. .

The composite material obtained by the above-mentioned method has a configuration in which the fiber material (F) layer is impregnated with the polyamide resin composition in the sheet cross-sectional shape, and both surfaces thereof are formed by the polyamide resin composition layer. ing.
Since such a composite material is made of a thermoplastic resin material, the composite material is used as it is or cut into a desired shape and size, and this is used as a molding material. It is possible to obtain a molded product.

  The resulting composite material has excellent elastic modulus, low warpage, little physical property deterioration under high temperature and high humidity, and excellent recycling characteristics, moldability and productivity compared to conventional thermosetting resins. Even if it is thin, it has excellent mechanical strength, so it can be reduced in weight when manufactured. The composite material of the present invention can be used for various parts and the like, and in particular, can be preferably used as a part of an electric / electronic device or an automobile part / member.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples / comparative examples.

[Materials used]
As the polyamide resin (A) in the present invention, one produced in the following production examples was used.
<Production Example 1 (Synthesis of polymetaxylylene sebacamide (MXD10))>
In a reaction can, sebacic acid (Ito Seiyaku, TA grade) was heated and melted at 170 ° C., and then the contents were stirred while metaxylylenediamine (Mitsubishi Gas Chemical Co., Ltd., MXDA) was sebacic acid. The temperature was raised to 240 ° C. while gradually dropping so that the molar ratio of to was 1: 1. After completion of dropping, the temperature was raised to 260 ° C. After completion of the reaction, the contents were taken out in a strand shape and pelletized with a pelletizer. The obtained pellets were charged into a tumbler and subjected to solid phase polymerization under reduced pressure to obtain a polyamide resin having an adjusted molecular weight.
The melting point of the polyamide resin (MXD10) measured by the following method is 191 ° C., the glass transition point is 60 ° C., the number average molecular weight is 30,000, and the oxygen transmission coefficient is 0.8 cc · mm / m ² · day · atm. there were.
Hereinafter, this polyamide resin is abbreviated as “MXD10”.

<Production Example 2 (Synthesis of polyparaxylylene sebacamide (PXD10))>
8950 g (44 mol) of sebacic acid (TA grade manufactured by Ito Oil Co., Ltd.) precisely weighed in a reaction vessel equipped with a stirrer, a partial condenser, a cooler, a thermometer, a dropping device and a nitrogen introduction tube, and a strand die, hypophosphorous acid Sodium monohydrate (13.401 g) (phosphorus atom concentration in the polyamide resin as 300 ppm) and sodium acetate (10.340 g) were weighed and charged. The molar ratio of sodium hypophosphite and sodium acetate is 1.0. After sufficiently purging the inside of the reaction vessel with nitrogen, the pressure was increased to 0.3 MPa with nitrogen, and the temperature was raised to 160 ° C. while stirring to uniformly melt sebacic acid.
Next, 6026 g (44 mol) of paraxylylenediamine (PXDA) was added dropwise over 170 minutes with stirring. During this time, the internal temperature was continuously raised to 281 ° C. In the dropping step, the pressure was controlled to 0.5 MPa, and the generated water was removed from the system through a partial condenser and a cooler. The temperature of the partial condenser was controlled in the range of 145 to 147 ° C. After completion of the dropwise addition of paraxylylenediamine, the pressure was reduced at a rate of 0.4 MPa / hr, and the pressure was reduced to normal pressure in 60 minutes. During this time, the internal temperature rose to 299 ° C. Thereafter, the pressure was reduced at a rate of 0.002 MPa / min, and the pressure was reduced to 0.08 MPa in 20 minutes. Thereafter, the reaction was continued at 0.08 MPa until the torque of the stirring device reached a predetermined value. The reaction time at 0.08 MPa was 10 minutes. Thereafter, the inside of the system was pressurized with nitrogen, and the polymer was taken out from the strand die and pelletized to obtain a polyamide resin. The obtained polyamide resin PXD10 had a melting point of 290 ° C. and a glass transition point of 75 ° C. The number average molecular weight was 25000, and the oxygen permeability coefficient was ^2.5 cc · mm / m ² · day · atm.
Hereinafter, this polyamide resin is abbreviated as “PXD10”.

<Production Example 3 (Synthesis of polymeta / paraxylylene sebacamide (MPXD10-1))>
In Production Example 1, the metaxylylenediamine was made into a 3: 7 mixture (molar ratio) of metaxylylenediamine and paraxylylenediamine, and the molar ratio of the mixed xylylenediamine to sebacic acid was gradually increased to 1: 1. The temperature was raised to 260 ° C. while dropping. After completion of dropping, a polyamide resin was obtained in the same manner as in Production Example 1 except that the temperature was raised to 280 ° C.
The melting point of the polyamide resin (MPXD10-1) measured by the method described below is 258 ° C., the glass transition point is 70 ° C., the number average molecular weight is 20,000, and the oxygen transmission coefficient is ² cc · mm / m ² · day · atm. Met.
Hereinafter, this polyamide resin is abbreviated as “MPXD10-1.”

<Production Example 4 (Synthesis of polymeta / paraxylylene sebacamide (MPXD10-2))>
A polyamide resin was obtained in the same manner as in Production Example 1 except that the metaxylylenediamine was a 7: 3 mixture (molar ratio) of metaxylylenediamine and paraxylylenediamine in Production Example 1.
The melting point of the polyamide resin (MPXD10-2) measured by the method described below is 215 ° C., the glass transition point is 63 ° C., the number average molecular weight is 28,000, and the oxygen permeability coefficient is 1.4 cc · mm / m ² · day.・ It was atm.
Hereinafter, this polyamide resin is abbreviated as “MPXD10-2”.

Other polyamide resins (A):
・ Polymetaxylylene adipamide (MXD6)
Product name "MX Nylon S6007" manufactured by Mitsubishi Gas Chemical
Melting point 240 ° C., glass transition point 85 ° C., number average molecular weight 40000, relative viscosity 2.65
Hereinafter, this polyamide resin is abbreviated as “MXD6”.

The following polyether copolymerized polyamide 12 was used as the polyether copolymerized polyamide resin (B).
Product name “UBESTA XPA 9055X1” manufactured by Ube Industries, Ltd.
Polyether copolymer polyamide 12, Shore D hardness 55, melting point 164 ° C
Hereinafter, this polyamide resin is abbreviated as “PE / N12”.

In addition, the measuring method of melting | fusing point of the said polyamide and a glass transition point (unit: degreeC) is as follows.
It measured by the differential scanning calorimetry (DSC) method using Shimadzu Corporation DSC-60. The measurement conditions are that a sample of about 5 mg is heated to 30 to 300 ° C. at 10 ° C./min, held at 300 ° C. for 2 minutes, and then cooled to 30 ° C. at a rate of 20 ° C./min. Next, the temperature was raised at 10 ° C./min, and the melting point and glass transition point were measured.

Moreover, the measurement of the number average molecular weight of each said XD10 and MXD6 is as follows.
It calculated | required as a PMMA conversion value by GPC measurement using Tosoh Co., Ltd. product HLC-8320GPC. Note that TSKgel SuperHM-H was used as the measurement column, hexafluoroisopropanol (HFIP) in which 10 mmol / L of sodium trifluoroacetate was dissolved was used as the solvent, and the measurement temperature was 40 ° C. A calibration curve was prepared by dissolving 6 levels of PMMA in HFIP.

Carbodiimide compound (C):
Alicyclic polycarbodiimide compound, manufactured by Nisshinbo Industries, Inc., trade name “Carbodilite LA-1”
Hereinafter, this carbodiimide compound is abbreviated as “carbodiimide”.
Stabilizer (D):
Copper chloride / potassium iodide mixture Copper chloride: potassium iodide = 1: 10 (mass ratio) mixture Hereinafter, abbreviated as “CuCl / KI”.
In addition, the usage-amount of the (C) and (D) component in Tables 1-2 is a mass part with respect to 100 mass of polyamide resin (A).

(Examples 1-5 and Comparative Examples 1-2)
Each of the above components is dry blended in the proportions shown in Tables 1 and 2 below (the proportion of each polyamide resin is mass%, the amount of additives is mass parts relative to 100 parts by mass of the resin components), and the cylinder diameter is 30 mm. To a single-screw extruder with a T-die (PTM-30, manufactured by Plastic Engineering Laboratory Co., Ltd.). After melt kneading under conditions of a cylinder temperature of 260 ° C. and a screw rotation speed of 30 rpm, the film-like product was extruded through a T die and solidified on a cooling roll to obtain a film having a thickness of 100 μm.
Various evaluations described below were performed using the obtained film. The results are shown in Tables 1-2.

(Examples 6-8 and Comparative Examples 3-5)
In Example 1, pellets of the polyamide resin composition were manufactured with the cylinder temperature at the time of pellet production being the melting point of each polyamide resin + 25 ° C., and the film was manufactured with the cylinder temperature at the time of film production being the melting point of each polyamide resin + 25 ° C. Except for the above, evaluation was performed in the same manner as in Example 1.
The evaluation results are shown in Table 2.

[Evaluation method]
In Examples and Comparative Examples, the measurement / evaluation methods are as follows.
(1) Tensile modulus (unit: MPa)
The tensile properties of the film were tested according to JIS K7127 and K7161, and the tensile modulus (MPa) was determined. In addition, the apparatus used the Toyo Seiki Co., Ltd. strograph, the test piece width | variety was 10 mm, the distance between chuck | zippers was 50 mm, the tensile speed was 50 mm / min, measurement temperature was 23 degreeC, and measurement humidity was 50% RH. .

(2) Tensile elongation (unit:%)
The tensile properties of the film were tested according to JIS K7127 and K7161, the strain at the time of film breakage was determined, and the value was taken as the tensile elongation. In addition, the apparatus used the Toyo Seiki Co., Ltd. strograph, the test piece width | variety was 10 mm, the distance between chuck | zippers was 50 mm, the tensile speed was 50 mm / min, measurement temperature was 23 degreeC, and measurement humidity was 50% RH. .

(3) Water absorption rate (unit:%)
After immersing the film in distilled water at 23 ° C. for 24 hours and wiping off the surface moisture, the film was heated with a Karl Fischer moisture meter at a temperature 10 ° C. lower than the melting point of the main component resin to measure the water absorption rate. Went.

(4) Oxygen transmission coefficient (unit: cc · mm / m ² · day · atm)
Under an atmosphere of 23 ° C. and 75% RH, the oxygen permeability coefficient (cc · mm / m ² · day · atm) of the film was measured according to JIS K7126. For the measurement, OX-TRAN2 / 21 manufactured by Modern Controls was used. It shows that gas-barrier property is so favorable that a value is low.

Example 9
[Manufacture of composite materials]
The PE / N12-containing MXD10 polyamide resin composition (referred to as MXD10-based polyamide) produced in Example 4 was melt-extruded with a single screw extruder having a 30 mmφ screw, and high-pressure low-density polyethylene (Nippon Polyethylene). Co., Ltd., trade name “NOVATEC UF421”) was melt-extruded with a single screw extruder having a 30 mmφ screw, co-extruded through a 500 mm wide T-die, and a 450 mm wide polyethylene layer (30 μm thick) ) / MXD10-based polyamide layer (25 μm thick) was obtained.
The obtained two-layer film is slit into a width of 400 mm and wound into a roll while peeling off the interface between the polyethylene layer and the MXD10-based polyamide layer. Each roll is MXD10-based polyamide having a length of 500 mm, a thickness of 25 μm, and a width of 400 mm. A single layer film was obtained.

While heating a sheet of carbon fiber (TR50S, tensile elastic modulus: 240 GPa) made by Mitsubishi Rayon Co., Ltd. in one direction so that the fiber basis weight is 125 g / m ² , while continuously heating to 210 ° C., the above The MXD10 polyamide single layer film was bonded to obtain a laminate.
Next, 10 laminates cut into 20 cm × 20 cm obtained were superposed to form a superposed product, and the MXD10-based polyamide single layer film was superposed on the carbon fiber layer side of the superposed product, and a mold at 260 ° C. Then, a hot press treatment was performed at a pressure of 1 MPa to obtain a plate-shaped molded product of MXD10-based polyamide on both surfaces. The obtained molded article had a carbon fiber content of 40% by volume. The obtained molded product was subjected to heat treatment at 130 ° C. for 4 minutes in a heating oven.
The obtained molded product was evaluated for tensile modulus, warpage, and modulus after hot water treatment.

The measurement and evaluation methods are as follows.
(1) Tensile elastic modulus: The molded product was formed into a 1 cm × 10 cm shape, and a tensile test was carried out according to JIS K7113.
(2) Warpage amount: The warpage amount at a point 10 cm from the center of the sample piece (20 cm × 20 cm) was measured. The warpage amount is obtained by subtracting the thickness of the sample piece from the maximum height of the sample piece. The smaller the amount of warping, the better the dimensional stability.
(3) Elastic modulus after hot water treatment: The molded product was shaped into 1 cm × 10 cm, immersed in boiling water at 100 ° C. for 240 hours, and then subjected to a tensile test.

The obtained molded article had a tensile elastic modulus of 100 GPa, a warpage amount of 0.5 mm, and a tensile elastic modulus after hot water treatment of 95 GPa.
As shown in Example 9, the composite material obtained by heating and pressing the laminate of the polyamide resin composition of the present invention and the fiber material (F) has an excellent elastic modulus and low warpage, It was found that there was little deterioration in physical properties under high temperature and high humidity, and it was excellent.

The polyamide resin composition of the present invention is a polyamide resin material having a high elastic modulus, a low water absorption rate, an excellent barrier property, and an improved flexibility. It can be suitably used for various molded products such as sheets, laminated films, laminated sheets, tubes, hoses, pipes, hollow containers, various containers such as bottles, and various parts.
In addition, the polyamide resin composition film and fiber material of the present invention are laminated and the laminate is heated and pressed, which is superior in recyclability, moldability and productivity compared to conventional thermosetting resins. Even if it is thin, it has excellent mechanical strength, so it can be reduced in weight when used as a product, and the resulting composite material can be used for various parts. Especially, parts for electric / electronic devices, automobile parts / members, etc. Can be preferably used.
As mentioned above, the polyamide resin composition of this invention can be preferably used in a wide field | area, and there exists a very high industrial applicability.

Claims (12)

  60 to 99% by mass of polyamide resin (A) in which 70 mol% or more of diamine structural units are derived from xylylenediamine and 50 mol% or more of dicarboxylic acid structural units are derived from sebacic acid or adipic acid, 12 units of polyamide Or the polyamide resin composition characterized by containing 40-1 mass% of polyether copolyamide (B) comprised from a polyamide 11 unit and a polyether unit.   The polyamide resin composition according to claim 1, wherein the xylylenediamine is metaxylylenediamine, paraxylylenediamine, or a mixture thereof.   Furthermore, 0.1-2 mass parts of carbodiimide compounds (C) are contained with respect to 100 mass parts of polyamide resin (A), The polyamide resin composition of Claim 1 or 2 characterized by the above-mentioned.   The polyamide resin composition according to claim 3, wherein the carbodiimide compound (C) is an aliphatic or alicyclic polycarbodiimide compound.   Furthermore, 0.01-1 mass part of stabilizer (D) is contained with respect to 100 mass parts of polyamide resin (A), The polyamide resin composition of any one of Claims 1-4 characterized by the above-mentioned. object.   The polyamide resin composition according to claim 5, wherein the stabilizer (D) is selected from an inorganic stabilizer, an aromatic secondary amine stabilizer, and an organic sulfur stabilizer.   The polyamide resin composition according to any one of claims 1 to 6, wherein the polyamide resin (A) is a polyamide resin obtained by polycondensation of metaxylylenediamine and sebacic acid.   The polyamide resin composition according to any one of claims 1 to 6, wherein the polyamide resin (A) is a polyamide resin obtained by polycondensation of metaxylylenediamine and adipic acid. The tensile elastic modulus (E) when formed into a film exhibits an elastic modulus of 70 to 97% with respect to the tensile elastic modulus (E _A ) formed when the polyamide resin (A) is formed into a film. The polyamide resin composition according to any one of 1 to 8.   A molded article formed by molding the polyamide resin composition according to any one of claims 1 to 9.   The molded article according to claim 10, wherein the molded article is a film, a sheet, or a tube.   A composite material obtained by laminating a film comprising the polyamide resin composition according to any one of claims 1 to 9 and a fiber material (F), and heating and pressurizing the laminate.