JP5853446B2 - 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 good gas barrier property, a low water absorption, a soft and excellent transparency.

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. Then, compared with the case of MXD6 polyamide alone, there existed a problem that gas barrier property fell. 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 has excellent elongation characteristics compared to MXD6 polyamide. It is expected to be used in various application fields. 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 rate, and being flexible and excellent in transparency.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a polyamide resin composed of xylylenediamine and sebacic acid (hereinafter sometimes referred to as “XD10 polyamide”) is copolymerized polyamide 6/66. / 12 or copolymer polyamide 6/66/11 copolymer polyamide (B) is blended in a specific amount, it is found that a polyamide resin composition suitable for the above purpose can be obtained, and the present invention is completed. It was.

  That is, according to the first invention of the present invention, polyamide resin (A) 100 in which 70 mol% or more of diamine structural units are derived from xylylenediamine and 50 mol% or more of dicarboxylic acid structural units is derived from sebacic acid. A polyamide resin composition comprising 1 to 40 parts by mass of copolymerized polyamide 6/66/12 or 6/66/11 (B) is provided with respect to parts by mass.

  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.

  Moreover, according to the 7th invention of this invention, the molded article formed by shape | molding the polyamide resin composition of the invention in any one of the 1st-6th is provided.

  Furthermore, according to an eighth invention of the present invention, in the seventh invention, there is provided a molded product characterized in that the molded product is a film, a sheet or a tube.

In the present invention, it has been found that XD10-based polyamide resin (A) and copolymerized polyamides 6/66/12 and 6/66/11 (B) are particularly well-suited, and these copolymerized polyamides When a specific amount of 1 to 40 parts by mass is blended with 100 parts by mass of the XD10-based polyamide resin (A), surprisingly, while exhibiting an excellent elastic modulus, extremely high tensile elongation is exhibited, and the gas barrier is soft. The present inventors have found that a polyamide resin material having excellent properties and transparency can be achieved. According to the present invention, a polyamide resin composition having a high elastic modulus, a good gas barrier property, a low water absorption rate, and being flexible and excellent in transparency can be obtained.
In particular, a molded product obtained using the polyamide resin composition of the present invention has a level of softness and transparency that could not be achieved by conventional techniques, and various types of films, sheets, tubes, etc. Expected to be used for various purposes.

  Since the polyamide resin composition of the present invention provides a polyamide resin material that is excellent in elastic modulus and gas barrier properties and hardly absorbs water, and is flexible and excellent in transparency, various films, sheets, laminated films, laminated sheets, tubes, It can be suitably used for various molded bodies such as various containers such as hoses, pipes, hollow containers, bottles, and various parts.

  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 are derived from xylylenediamine and 50 mol% or more of the dicarboxylic acid structural units is derived from sebacic acid is used.

The polyamide resin (A) contains a diamine component containing xylylenediamine at 70 mol% or more, preferably 80 mol% or more, and sebacic acid at 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more. It can be obtained by polycondensation of a dicarboxylic acid component.
If the xylylenediamine is less than 70 mol%, the polyamide resin composition finally obtained has insufficient barrier properties. If the sebacic acid is less than 50 mol%, the polyamide resin composition becomes hard and the workability is low. Deteriorate.
As the xylylenediamine, it is preferable to use metaxylylenediamine, paraxylylenediamine or a mixture thereof. When mixed and used, it can be used in any proportion, 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 used as the raw material dicarboxylic acid component of the polyamide resin (A) is 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol% or more.
As the raw material dicarboxylic acid component other than sebacic acid, α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms other than sebacic acid can be preferably used. For example, succinic acid, glutaric acid, pimelic acid, suberic acid, Examples include aliphatic dicarboxylic acids such as azelaic acid, adipic acid, undecanedioic acid, and dodecanedioic acid, and one or a mixture of two or more types can be used. Adipic acid is particularly preferred because it is in an appropriate range.

As dicarboxylic acid components other than sebacic acid, aromatic dicarboxylic acids 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, 2,6- Naphthalene dicarboxylic acid such as isomers such as naphthalene dicarboxylic acid and 2,7-naphthalene dicarboxylic acid is 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 dicarboxylic acid other than α, ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms is used as the dicarboxylic acid component other than sebacic acid, isophthalic acid should be used from the viewpoint of molding processability and barrier properties. Is preferred. 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. It is not 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 xylylenediamine and sebacic acid is polymerized in a molten state while raising the temperature under pressure in the presence of water and removing the added water and condensed water. It can also be produced by a method in which xylylenediamine is directly added to molten sebacic acid and polycondensed under normal pressure. In this case, in order not to solidify the reaction system, xylylenediamine is continuously added, and the reaction system is heated up so that the reaction temperature is higher than the melting point of the generated oligoamide and polyamide, while the reaction system is heated. Condensation 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 to 310 ° C, more preferably 160 to 300 ° C, and 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 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 copolymerized polyamide (B) described later can be measured by a differential scanning calorimetry (DSC) method. This refers to the melting point and glass transition point measured by raising the temperature again after eliminating the influence of the history on 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 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, 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 using a phosphorus compound, it is contained in the polyamide resin (A) so that the phosphorus atom concentration in the polyamide resin composition (A) is 200 ppm or less, preferably 160 ppm or less, more preferably 100 ppm or less. desirable.
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, copolymer polyamide 6/66/12 (B-1) or copolymer polyamide 6/66/11 or (B-2) is blended as copolymer polyamide (B) to be blended with polyamide resin (A). To do.

Copolymer polyamide 6/66/12 (B-1) is a ternary system comprising polyamide 6 units (capramide units) and polyamide 66 units (hexamethylene adipamide units) and polyamide 12 units (dodecanamide units). It is a copolymerized polyamide of the original system or higher.
Copolymer polyamide 6/66/12 (B-1) is composed of polyamide 6-forming components such as caprolactam, polyamide 66-forming components such as hexamethylenediamine and adipic acid, and 12-aminododecanoic acid or dodecane lactam. From the polyamide 12-forming component, if necessary, it can be obtained by copolymerization using other polycondensation raw materials.

  The copolymerization ratio of the copolymerized polyamide 6/66/12 (B-1) is preferably 60 to 95% by mass of polyamide 6 units, more preferably 70 to 90% by mass, and further preferably 75 to 85% by mass. The polyamide 66 unit is 0.5 to 25% by mass, more preferably 1 to 20% by mass, still more preferably 5 to 15% by mass, and the polyamide 12 unit is 0.5 to 25% by mass, more preferably, 1-15 mass%, More preferably, it is 3-10 mass%. When the copolymerization ratio of the copolymerized polyamide 6/66/12 (B-1) is within the above range, the mixing property with the polyamide resin (A) becomes good, and the resin composition is excellent in transparency, flexibility and the like. It tends to be easy to obtain.

Further, the copolymerized polyamide 6/66/12 (B-1) is not necessarily limited to the ternary copolymer, and is a quaternary or higher copolymer including other copolymer units. Also good.
As such a polyamide component, an aliphatic amide component is preferable, and polyamide 11 (polyundecanamide), polyamide 9 (poly-ω-aminononanoic acid), polyamide 46 (polytetramethylene adipamide), polyamide 610 (polyhexahexanamide). Preferred examples include aliphatic amide components such as methylene sebacamide).
Moreover, the copolymer which added aromatic dicarboxylic acid components, such as a terephthalic acid and isophthalic acid, and aromatic diamine components, such as a xylylenediamine, may be sufficient.

There is no restriction | limiting in the method to manufacture copolyamide 6/66/12, A conventionally well-known method is applicable. As a polymerization method, a known method such as melt polymerization, solution polymerization, solid phase polymerization or the like can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations.
For example, the lactam component, diamine component, dicarboxylic acid component, or these may be in the form of a salt, and water is further heated to 180-220 ° C. in an autoclave and kept under pressure for a predetermined time to amide. After that, the pressure is returned to normal pressure, the temperature is raised again to 210 to 260 ° C., and after maintaining for a predetermined time, a copolymerized polyamide can be obtained.
Copolymer polyamide 6/66/12 is commercially available, and may be appropriately selected from these.

The copolymerized polyamide 6/66/11 (B-2) used in the present invention is composed of a polyamide 6 unit (capramide unit), a polyamide 66 unit (hexamethylene adipamide unit), and a polyamide 11 unit (undecanamide unit). Is a ternary or quaternary or higher copolymer polyamide.
The copolymerized polyamide 6/66/11 (B-2) is composed of a polyamide 6-forming component such as caprolactam, a polyamide 66-forming component such as hexamethylenediamine and adipic acid, and 11-aminoundecanoic acid or undecane lactam. From the polyamide 11-forming component, it can be obtained by copolymerization using other polycondensation raw materials if necessary.

  The copolymerization ratio of the copolymerized polyamide 6/66/11 (B-2) is preferably 60 to 95% by mass of polyamide 6 units, more preferably 70 to 90% by mass, and further preferably 75 to 85% by mass. The polyamide 66 unit is 0.5 to 25% by mass, more preferably 1 to 20% by mass, still more preferably 5 to 15% by mass, and the polyamide 11 unit is 0.5 to 25% by mass, more preferably 1 -15% by mass, more preferably 3-10% by mass. When the copolymerization ratio of the copolymerized polyamide 6/66/11 (B-2) is in the above range, the mixing property with the polyamide resin (A) becomes good, and the resin composition is excellent in transparency, flexibility and the like. It tends to be easy to get.

Further, the copolymerized polyamide 6/66/11 (B-2) is not necessarily limited to the ternary copolymer, and is a quaternary or higher copolymer including other copolymer units. Also good.
As such a polyamide component, an aliphatic amide component is preferable. Polyamide 12 (polydodecanamide), polyamide 9 (poly-ω-aminononanoic acid), polyamide 46 (polytetramethylene adipamide), polyamide 610 (polyhexahexanamide) Preferred examples include aliphatic amide components such as methylene sebacamide).
Moreover, the copolymer which added aromatic dicarboxylic acid components, such as a terephthalic acid and isophthalic acid, and aromatic diamine components, such as a xylylenediamine, may be sufficient.

There is no restriction | limiting in the method to manufacture copolyamide 6/66/11, A conventionally well-known method is applicable. As a polymerization method, a known method such as melt polymerization, solution polymerization, solid phase polymerization or the like can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations.
For example, the lactam component, diamine component, dicarboxylic acid component, or these may be in the form of a salt, and water is further heated to 180-220 ° C. in an autoclave and kept under pressure for a predetermined time to amide. After that, the pressure is returned to normal pressure, the temperature is raised again to 210 to 260 ° C., and after maintaining for a predetermined time, a copolymerized polyamide can be obtained.

The above-mentioned copolymer polyamides (B-1) and (B-2) preferably have a terminal amino group concentration of 1 to 100 μeq / g, more preferably 2 to 50 μeq / g, and a terminal carboxyl group concentration. Is preferably 1 to 100 μeq / g, more preferably 2 to 50 μeq / g. 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 number average molecular weight of the copolymerized polyamides (B-1) and (B-2) 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 to 4.0.

  The polyamide resin composition of the present invention comprises 1 to 100 parts by mass of the polyamide resin (A), the copolymerized polyamide (B) (that is, the sum of (B-1) and / or (B-2)) If the amount is less than 1 part by mass, the improvement in elongation is insufficient and flexibility cannot be obtained, and if it exceeds 40 parts by mass, the strength, elastic modulus and transparency are lowered, and the water absorption is reduced. To rise. The preferred content is 5 to 35 parts by mass, more preferably 10 to 30 parts 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 copolymerized polyamide (B) becomes easy 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 content of the carbodiimide compound (C) is 0.1 to 2 parts by mass, preferably 0.2 to 1.5 parts by mass, and more preferably 0.3 to 100 parts by mass of the polyamide resin (A). -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.

  As the aromatic secondary amine stabilizer, a compound having a diphenylamine skeleton, a compound having a phenylnaphthylamine skeleton, and a compound having a dinaphthylamine skeleton are preferable, and a compound having a diphenylamine skeleton and a compound having a phenylnaphthylamine skeleton are 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 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 copolymerized polyamide (B) as long as the effects of the present invention are not impaired. 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 copolymerized polyamide (B), polyester resin, polycarbonate resin, polyimide resin, polyurethane resin, acrylic resin, polyacrylonitrile, ionomer, ethylene-vinyl acetate Examples thereof include polymers, 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, ultraviolet absorbers, impact modifiers and other well-known additives can be blended.

  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.

The method for producing the polyamide resin composition of the present invention is not particularly limited, and the polyamide resin (A), the copolymerized polyamide (B), and if necessary, the carbodiimide compound (C) and other components may be added in any order. Can be produced by mixing and kneading. 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.
The film obtained from the polyamide resin composition of the present invention exhibits a high level of practical physical properties, and has a tensile elastic modulus of 1000 to 2500 MPa, a tensile elongation of 200 to 500%, and an oxygen transmission coefficient of 0.5 to 3.5 cc · mm / m. ² · day · atm, water absorption 0.1 to 1.0%, haze 0.5 to 20.0%.
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-die is cooled and solidified by casting with a chilled roll, and a die to a tube having an annular slit. Examples include an inflation method 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 formed in this manner 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 specified, but the thickness of the polyamide resin monolayer is preferably 2 to 100 μm for an unstretched film and 2 to 50 μm for a stretched film / sheet, and is a laminated film. / The thickness of the entire sheet is about 10 to 300 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 mm to 2 mm. If the wall thickness is less than 0.1 mm, the shape of the tube cannot be maintained. On the other hand, if the wall thickness exceeds 2 mm, it becomes hard and the flexibility of the tube is lost, which makes it difficult to assemble the product.

  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 comprises at least one layer comprising the polyamide resin composition of the present invention, and is a 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.

  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”.

The following polyamides (B-1) and (B-2) were used as the copolymerized polyamide (B) in the present invention.
(B-1) Copolymer polyamide 6/66/12
Product name "Ube Nylon 6434B", manufactured by Ube Industries, Ltd.
Melting point 190 ° C., glass transition point 44 ° C., relative viscosity 4.05 (in 96% sulfuric acid, resin concentration 1
g / 100cc, measured at a temperature of 25 ° C)
Hereinafter, this polyamide resin is abbreviated as “6/66/12”.

(B-2) Copolymer polyamide 6/66/11
A 70 L autoclave was charged with 17 kg of ε-caprolactam, 6 kg of 50% aqueous solution of hexamethyleneammonium adipate, and 1 kg of aminoundecanoic acid. The inside of the polymerization tank was purged with nitrogen, then sealed and heated to 180 ° C. Then, the temperature in the polymerization tank was raised to 240 ° C. while adjusting the pressure in the polymerization tank to 17.5 kgf / cm ² G while stirring. Two hours after the polymerization temperature reached 240 ° C., the pressure in the polymerization tank was released to normal pressure over about 2 hours. After releasing the pressure, polymerization was carried out for 1 hour under a nitrogen stream, and then vacuum polymerization was carried out for 2 hours. After introducing nitrogen and returning to normal pressure, the stirrer was stopped, the strand was extracted as a strand and pelletized, and the unreacted monomer was extracted and removed using boiling water and dried. The relative viscosity of the obtained copolymer polyamide (measured at 96% sulfuric acid, resin concentration of 1 g / 100 cc, temperature of 25 ° C.) was 3.8.
Hereinafter, this polyamide resin is abbreviated as “6/66/11”.

Other polyamide resin components:
・ Polyamide 6/66
Product name "Ube Nylon 5033B", manufactured by Ube Industries, Ltd.
Melting point 196 ° C, glass transition point 46 ° C
Relative viscosity 4.08 (measured in 96% sulfuric acid, resin concentration 1 g / 100 cc, temperature 25 ° C.)
Hereinafter, this polyamide resin is abbreviated as “N6 / 66”.

・ Polyamide 6
Product name "Ube Nylon 1022B", manufactured by Ube Industries, Ltd.
Melting point 220 ° C., glass transition point 45 ° C., number average molecular weight 22,000
Relative viscosity 3.37 (measured in 96% sulfuric acid, resin concentration 1 g / 100 cc, temperature 25 ° C.)
Hereinafter, this polyamide resin is abbreviated as “N6”.

・ Polyamide 11
Product name "Rilsan BESN OTL", manufactured by Arkema
Melting point 188 ° C., glass transition point 40 ° C., number average molecular weight 27,000
Hereinafter, this polyamide resin is abbreviated as “N11”.

・ Polyamide 12
Product name “UBESTA3030U” manufactured by Ube Industries, Ltd.
Melting point 178 ° C., glass transition point 50 ° C., number average molecular weight 30,000
Hereinafter, this polyamide resin is abbreviated as “N12”.

Carbodiimide compound (C) component:
Alicyclic polycarbodiimide compound, manufactured by Nisshinbo Industries, Inc., trade name “Carbodilite LA-1”
Hereinafter, this carbodiimide compound is abbreviated as “carbodiimide”.

Modified elastomer component:
Maleic acid-modified ethylene-propylene copolymer, trade name “Tuffmer MP0610” manufactured by Mitsui Chemicals, Inc.
Hereinafter, it is abbreviated as “modified EPR”.

Stabilizer:
Copper chloride / potassium iodide mixture Copper chloride: potassium iodide = 1: 10 (mass ratio) mixture Hereinafter, abbreviated as “CuCl / KI”.

(Examples 1-5 and Comparative Examples 1-8)
Each of the above components was dry blended in the proportions shown in Tables 1 and 2 below (all expressed in parts by mass), and the resulting dry blend was measured at a rate of 15 kg / hr using a weighing feeder at a cylinder diameter of 37 mm. Then, it was fed to a twin screw extruder equipped with a kneading type screw having a kneading disk. Melt kneading was performed under conditions of a cylinder temperature of 230 ° 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 into a twin-screw extruder with a T-die having a cylinder diameter of 30 mm (PTM-30, manufactured by Plastic Engineering Laboratories) at a rate of 1.2 kg / hr with a weighing feeder. After extruding at a cylinder temperature of 230 ° C. and a screw rotation speed of 50 rpm, the film-like material is extruded through a T-die and solidified on a 60 ° C. cooling roll while being drawn at a speed of 2.7 m / min. Obtained.
Various evaluations described below were performed using the obtained film.
The evaluation results are shown in Tables 1-2.

(Examples 6 to 8)
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 1.

[Evaluation method]
In Examples and Comparative Examples, the measurement / evaluation methods are as follows.

(1) Oxygen permeability 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. The lower the value, the better the gas barrier property.

(2) Melting point of polyamide, glass transition point (unit: ° C)
It calculated | required 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.

(3) Number average molecular weight The number average molecular weight was calculated | required as a PMMA conversion value by GPC measurement using Tosoh Co., Ltd. product HLC-8320GPC. In addition, TSKgel SuperHM-H was used for the measurement column, hexafluoroisopropanol (HFIP) in which 10 mmol / l 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. In addition, the number average molecular weight of N6, N11, and N12 is a manufacturer's nominal value.

(4) Haze (Unit:%)
About the film, Nippon Denshoku Industries Co., Ltd. make, color difference and turbidity measuring device COH-300A were used, and the haze of the film was measured according to ASTMD1003.

(5) 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.

(6) 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. .

(7) Tensile elongation (unit:%)
The tensile properties of the film were tested according to JIS K7127 and K7161, and the tensile fracture strain at the time of film breakage, the nominal strain at the time of tensile fracture, and the nominal strain at the time of tensile strength were obtained, 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. .

(8) Hydrolysis resistance and heat aging resistance (Unit:%)
First, the film was heat-treated at 110 ° C. for 48 hours with a hot air dryer. Next, the treatment for 24 hours was performed in boiling water (100 ° C.). The tensile properties of the film before and after processing are JIS
Tests were performed according to K7127 and K7161, and the stress at break (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. .
The ratio of stress at break before and after heat treatment was defined as the tensile strength retention rate, and the tensile strength retention rate (%) was calculated from the following formula (1). The higher the tensile strength retention rate, the better the hydrolysis resistance and heat aging resistance.
Tensile strength retention rate (%) = [stress at break of film after heat treatment (MPa) / stress at break of film before heat treatment (MPa)] × 100 (1)

As apparent from Table 1 and Table 2 above, the films of Examples 1 to 5 in which a predetermined amount of copolymerized polyamide 6/66/12 or 6/66/11 was blended with xylylene sebacamide were blended with this. The tensile elongation is 2 to 3 times or more while maintaining the elastic modulus at a high level as compared with Comparative Example 1 that is not, and it can be seen that the film is extremely soft, that is, has both hardness and softness. In addition, it can be seen that the films of Examples 6 to 8 also show a high level of practical physical properties and exhibit the effects of the present invention. On the other hand, the film of Comparative Example 2 in which the copolymerized polyamide 6/66/12 is blended in excess of 40 parts by mass has a large decrease in elastic modulus compared to the unblended film and is less than half, and the degree of decrease in gas barrier properties. It can be seen that the water absorption rate is large.
In Comparative Examples 3 and 4 using polyamide 6/66 as the copolymerized polyamide, it can be seen that the tensile elongation is not as high as that of the example. Similarly, when other polyamides are blended, the tensile elongation is poor (Comparative Example 6), the transparency (haze) is poor (Comparative Examples 5, 7 and 8), and the modified EPR has a poor haze and an elastic modulus. It turns out that it halves (Comparative Example 5).

  Since the polyamide resin composition of the present invention is a polyamide resin material having a high elastic modulus, good gas barrier properties, low water absorption, flexible and excellent transparency, various films, sheets, laminated films, laminated sheets It can be suitably used for various molded articles such as various containers such as tubes, hoses, pipes, hollow containers and bottles, and various parts.

Claims (7)

Copolymer polyamide 6/66/12 with respect to 100 parts by mass of polyamide resin (A) in which 70 mol% or more of diamine structural units are derived from xylyldiamine and 50 mol% or more of dicarboxylic acid structural units are derived from sebacic acid. Alternatively, an extrusion-molded product formed by molding a polyamide resin composition containing 1 to 40 parts by mass of 6/66/11 (B). The extruded product obtained by molding 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 is shape | molded, Extruded product that becomes . The extruded product obtained by molding the polyamide resin composition according to claim 3, wherein the carbodiimide compound (C) is an aliphatic or alicyclic polycarbodiimide compound. Additionally, stabilizer (D), relative to the polyamide resin (A) 100 parts by mass of the polyamide resin composition according to any of claims 1 to 4, characterized in that it contains 0.01 to 1 parts by weight Extrusion product formed by molding . Stabilizer (D) is an inorganic stabilizer, obtained by molding the polyamide resin composition according to claim 5, characterized in that it is selected from an aromatic secondary amine-based stabilizers and organic sulfur type stabilizer Extruded product . Extrusion is, films, extrusion molded article according to claim 1 is a sheet or tube.