JP2006297894A - Polyamide laminated biaxially oriented film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide laminated biaxially oriented film which exhibits gas barrier nature, bending fatigue resistance, transparency and is almost free from the electrostatic attachment of a powdered matter, a dust, etc., is small in the humidity dependency, and thus is suitable for a food packaging to which the antistatic nature being maintained for a long period of time is given. <P>SOLUTION: The polyamide laminated biaxially oriented film comprises the following (a) layer, and (b) layer and/or (c) layer. The (a) layer contains a half-aromatic polyamide (A) obtained from m- and/or p-xylilene diamine and an aliphatic dicarboxylic acid. The (b) layer comprises an aliphatic polyamide resin composition (B) consisting of an aliphatic polyamide (B1) and the following polyether ester amide elastomer (B2). The B2 contains a polyamide hard segment (b1) consisting of the same polyamide formation units as those of B1 and a dicarboxylic acid, a soft segment consisting of a specific polyalkylene oxide (b2), and an electrolyte salt compound (b3). The (c) layers is a layer containing a half aromatic polyamide (A) and an aliphatic polyamide resin composition (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is for food packaging that has gas barrier properties, bending fatigue resistance, transparency, resistance to electrostatic adhesion of powder, dust, etc., low humidity dependency, and long-lasting antistatic properties. The present invention relates to a suitable polyamide laminated biaxially stretched film.

  Polyamide resin has excellent strength, flexibility, heat resistance, chemical resistance, and excellent gas barrier properties, so it can be used for food packaging such as raw meat, konjac, and pickles, and medical packaging such as medical infusions. Widely used in containers for agricultural chemicals and reagents. However, depending on the application, the gas barrier properties are not always sufficient, and various methods for improving the gas barrier properties of packaging materials, containers and the like have been proposed.

  One method for improving the gas barrier property is, for example, a method of laminating a resin having a good gas barrier property with an aliphatic polyamide. In particular, many methods using semi-aromatic polyamides whose main component is a polyamide constituent unit composed of m- and / or p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms have been studied.

  For example, Patent Document 1 and Patent Document 2 disclose a polyamide laminated film having improved bending fatigue due to repeated bending fatigue.

  On the other hand, a film made of polyamide resin has a high electrical resistivity and is easily charged. Therefore, the charged electricity cannot be leaked, and dust adheres to the surface, troubles when filling contents, and sink marks during printing. Various failures caused by static electricity occur. In recent years, at the time of secondary processing using these films, with the increase in processing speed, problems due to insufficient antistatic properties have become apparent, and improvements are desired.

  As a method for improving the antistatic property, a method is known in which a surfactant or the like is applied to the surface, or a low molecular weight antistatic agent such as a water-absorbing compound such as polyalkylene oxide or an alkylamine is kneaded into a resin. However, antistatic agents such as surfactants, polyalkylene oxides and alkylamines are excellent in the initial antistatic property, but are easy to bleed out and have poor water resistance, so the antistatic effect does not last for a long time. Has the disadvantages. In addition, the dependence of the antistatic effect on humidity is very large.

  For example, Patent Document 3 and Patent Document 4 disclose polyether ester amides mainly composed of polyamide and polyoxyalkylene glycol as methods for improving the durability of the antistatic effect and reducing the humidity dependence of the antistatic effect. A method of blending an elastomer with a thermoplastic resin is disclosed.

JP 05-000492 A, Japanese Patent Laid-Open No. 05-064868 Japanese Patent Laid-Open No. 60-023435 JP-A-60-170646

  The present invention has gas barrier properties, flexural fatigue resistance, transparency, and is difficult to electrostatically adhere powders and dusts, has low humidity dependence, and is provided with antistatic properties that last for a long time. An object of the present invention is to provide a polyamide-laminated biaxially stretched film that is optimized.

The polyamide laminated biaxially stretched film of the present invention is a laminated film of at least two layers obtained by laminating the following (a) layer and at least one layer selected from the following (b) layer and the following (c) layer. The present invention provides a polyamide-laminated biaxially stretched film characterized by being biaxially stretched.
(A) Layer: 70 mol% or more of a polyamide constituent unit derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain The layer containing the semi-aromatic polyamide (A) to contain.
(B) Layer: A layer comprising an aliphatic polyamide resin composition (B) comprising 70 to 98% by weight of aliphatic polyamide (B1) and 30 to 2% by weight of the following polyetheresteramide elastomer (B2).
(B) Polyether ester amide elastomer (B2) of the layer: containing 60% by weight or more of the same polyamide forming unit as the aliphatic polyamide (B1), among aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid A polyamide hard segment (b1) comprising at least one dicarboxylic acid selected from:
A soft segment (b2) comprising a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5,000;
A polyetheresteramide elastomer comprising an electrolyte salt compound (b3),
A polyether ester amide elastomer containing 0.01 to 10% by weight of (b3) with respect to the total weight (100% by weight) of (b1) and (b2).

（式中、Ｑは炭素数２〜４のアルキレン基、ｎは１〜５０の整数を表す。）
（ｃ）層： 半芳香族ポリアミド（Ａ）と脂肪族ポリアミド樹脂組成物（Ｂ）とを含む層。

(In the formula, Q represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 50.)
(C) Layer: A layer containing a semi-aromatic polyamide (A) and an aliphatic polyamide resin composition (B).

The preferable aspect of the polyamide laminated biaxially stretched film of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (B1) is a homopolymer composed of at least one polyamide-forming unit selected from the group consisting of caprolactam, dodecane lactam, 12-aminododecanoic acid and hexamethylenediamine / adipate, or a copolymer thereof. Be a polymer.
[2] At least one kind selected from the group consisting of adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate as the dicarboxylic acid of the polyamide hard segment (b1) of the polyetheresteramide elastomer (B2) It must be a dicarboxylic acid.
[3] The polyalkylene oxide of the soft segment (b2) is an alkylene group in which Q in the general formula (1) is 2 and / or 3.
[4] In the polyamide laminated biaxially stretched film, both outer layers are layers selected from the (b) layer and the (c) layer, and are at least three layers.

  The polyamide laminated biaxially stretched film of the present invention has gas barrier properties, flexural fatigue resistance, transparency, and is less susceptible to electrostatic adhesion of powder, dust, etc., has low humidity dependency, and has long-lasting antistatic properties. The balance of performance is optimized. Therefore, it is useful as a film for food packaging, medical treatment, and medicine packaging that dislikes alteration of contents due to oxygen, and because of problems caused by static electricity, the range of use that has been limited so far will be expanded. The value is extremely great.

  The semi-aromatic polyamide (A) of the layer (a) is a polyamide structural unit derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms. Is a semi-aromatic polyamide containing 70 mol% or more in the molecular chain.

The semi-aromatic polyamide (A) is a polyamide structural unit derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain. It is contained in a range of 70 mol% or more, preferably 75 mol% or more, more preferably 80 mol% to 100 mol%. When the ratio of the specific polyamide constituent unit in the molecular chain of the semi-aromatic polyamide (A) is less than 70 mol%, the oxygen gas barrier property of the obtained laminated biaxially stretched film is lowered, for example, at a temperature of 25 ° C, relative Since it is difficult to obtain a product of 15 cc / (m ² · 24 h · atm) or less under a humidity of 65%, it is not preferable.

Examples of units derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, 2-methyladipic acid, 2,2 -Units derived from dimethylglutaric acid, 2,2,4 / 2,4,4-trimethyladipic acid, 2-butylsuberic acid. Among the units derived from the above aliphatic dicarboxylic acids, units derived from adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid are preferable, and units derived from adipic acid are more preferable.
The semi-aromatic polyamide (A) has 70 molecular units composed of xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain. As long as it contains at least mol%, it is possible to copolymerize other polyamide constituent units excluding the polyamide constituent units.
Semi-aromatic polyamide (A), other polyamides excluding xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and polyamide structural units derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms Examples of the structural unit include a diamine unit other than a unit derived from xylylenediamine, a dicarboxylic acid unit other than a unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and other units.
Examples of diamine units other than those derived from xylylenediamine include hexamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, 2 / 3-methyl-1,5-pentanediamine, 2- Aliphatic diamines such as methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine, bis (4-aminocyclohexyl) propane, Bis (3-methyl-4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1 , 3,3-Trimethylcyclohexanemethylamine (isophorone diamine) ), Alicyclic diamines such as bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, tricyclodecanedimethylamine, and aromatic diamines such as p-bis- (2-aminoethyl) benzene. Units are listed. These can use 1 type (s) or 2 or more types.
Examples of dicarboxylic acid units other than those derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, tridecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosanedicarboxylic acid. Examples thereof include units composed of acids, alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. These can use 1 type (s) or 2 or more types.
Examples of other units include units composed of lactams such as caprolactam, aliphatic aminocarboxylic acids such as 12-aminododecanoic acid, and aminocarboxylic acids such as aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types.

  Specific examples of the semi-aromatic polyamide (A) include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene pimeramide (polyamide MXD7), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azease. Lamidamide (polyamide MXD9), polymetaxylylene sepacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene azelamide (polyamide PXD9), etc. Homopolymer, metaxylylene / paraxylylene adipamide copolymer, metaxylylene / paraxylylene piperamide copolymer, metaxylylene / paraxylylene speramide copolymer, metaxylylene / paraxylylene azelamide Polymer, m-xylylene / para-xylylene cepa Kami-de copolymers, m-xylylene / para-xylylene dodecanediamide copolymer copolymers thereof.

  The relative viscosity of the semiaromatic polyamide (A) measured according to JIS K-6920 is preferably 1.8 to 3.5, more preferably 2.0 to 3.0. When the relative viscosity is less than the above value, the mechanical properties of the resulting film may be lowered. On the other hand, when the relative viscosity exceeds the above value, the viscosity at the time of melting increases, and it may be difficult to form a film.

  The aliphatic polyamide resin composition (B) is a composition comprising 70 to 98% by weight of aliphatic polyamide (B1) and 30 to 2% by weight of a polyetheresteramide elastomer (B2), preferably aliphatic polyamide (B1). A composition comprising 75 to 97% by weight and 25 to 3% by weight of a polyetheresteramide elastomer (B2), more preferably 80 to 97% by weight of an aliphatic polyamide (B1) and 20 to 20% of a polyetheresteramide elastomer (B2) 3% by weight (the total weight of the aliphatic polyamide (B1) and the polyetheresteramide elastomer (B2) is 100% by weight).

The aliphatic polyamide (B1) of the aliphatic polyamide resin composition (B) has an amide bond (—CONH—) in the main chain and is composed of an aliphatic polyamide forming unit.
The aliphatic polyamide (B1) is polymerized by a known method such as melt polymerization, solution polymerization or solid phase polymerization using a lactam, an aminocarboxylic acid, and / or a nylon salt composed of an aliphatic diamine and an aliphatic dicarboxylic acid as a raw material. Or by copolymerization.

  Examples of the lactam of the aliphatic polyamide (B1) include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. These can use 1 type (s) or 2 or more types.

  Examples of the aminocarboxylic acid of the aliphatic polyamide (B1) include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. These can use 1 type (s) or 2 or more types.

  Examples of the aliphatic diamine constituting the nylon salt of the aliphatic polyamide (B1) include ethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, peptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, Decamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptacamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2 / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 5-methyl 1,9-nonanediamine, and the like. These can use 1 type (s) or 2 or more types.

  Examples of the aliphatic dicarboxylic acid constituting the nylon salt of the aliphatic polyamide (B1) include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, and tetradecanedicarboxylic acid. Pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid and the like. These can use 1 type (s) or 2 or more types.

  Specific examples of the aliphatic polyamide (B1) include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene adipa Amide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), poly Hexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene undecamide (poly) 911), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene dodeca Amide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), etc. Examples thereof include a polymer and a copolymer using several kinds of raw material monomers forming these. These can use 1 type (s) or 2 or more types.

  The aliphatic polyamide (B1) is a homopolymer or copolymer comprising at least one polyamide-forming unit selected from the group consisting of caprolactam, dodecane lactam, 12-aminododecanoic acid, and hexamethylenediamine / adipate. Are preferred, that is, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polydodecanamide (polyamide 12), polyamide 6/66 copolymer (copolymer of polyamide 6 and polyamide 66, Hereinafter, the copolymer is described in the same manner), a polyamide 6/12 copolymer, and a polyamide 6/66/12 copolymer are preferable.

  The relative viscosity of the aliphatic polyamide (B1) measured according to JIS K-6920 is preferably 2.0 to 5.0, and more preferably 2.5 to 4.5. When the relative viscosity of the aliphatic polyamide (B1) is less than the above value, the mechanical properties of the resulting film may be lowered. On the other hand, when the relative viscosity of the aliphatic polyamide (B1) exceeds the above value, the viscosity at the time of melting becomes high and it may be difficult to form a film.

  There are no particular restrictions on the type, concentration and molecular weight distribution of the end groups of the aliphatic polyamide (B1), and monoamines, diamines, monocarboxylic acids, dicarboxylic acids are used for molecular weight adjustment and melt stabilization during molding processing. One or two or more of them can be added in appropriate combination. Examples thereof include amines such as laurylamine, stearylamine, hexamethylenediamine, and metaxylylenediamine, and carboxylic acids such as acetic acid, stearic acid, benzoic acid, adipic acid, isophthalic acid, and terephthalic acid. The amount of these molecular weight regulators to be used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the finally obtained polyamide falls within the above range.

The polyether ester amide elastomer (B2) of the aliphatic polyamide resin composition (B) contains 60% by weight or more of the same polyamide-forming unit as the aliphatic polyamide (B1), and includes an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and A polyamide hard segment (b1) comprising at least one dicarboxylic acid selected from aromatic dicarboxylic acids;
A soft segment (b2) comprising a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5,000;
A polyetheresteramide elastomer comprising an electrolyte salt compound (b3),
A polyether ester amide elastomer containing 0.01 to 10% by weight of (b3) with respect to the total weight of (b1), (b2) and (b3).

（式中、Ｑは炭素数２〜４のアルキレン基、ｎは１〜５０の整数を表す。）

(In the formula, Q represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 50.)

The polyamide hard segment (b1) of the polyetheresteramide elastomer (B2) is a polyamide having carboxyl groups at both terminal groups, and the same polyamide forming unit as the aliphatic polyamide (B1) is 60% by weight or more, preferably 70%. % By weight or more, more preferably 75% by weight or more, and particularly preferably 80% by weight or more, and is obtained from at least one dicarboxylic acid selected from aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid. Is.
In the polyamide hard segment (b1) of the polyetheresteramide elastomer (B2), the same polyamide-forming unit as the aliphatic polyamide (B1) includes the lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic dicarboxylic acid. And a unit composed of a nylon salt.
In the polyamide hard segment (b1) of the polyether ester amide elastomer (B2), a film having excellent transparency can be obtained by containing 60% by weight or more of the same polyamide forming unit as the aliphatic polyamide (B1).

  The dicarboxylic acid in the polyamide hard segment (b1) is used as a molecular weight modifier, and in the presence thereof, a polyamide having both carboxyl groups is obtained by ring-opening polymerization or polycondensation of the polyamide-forming unit by a conventional method. . Dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, dicyclohexylmethane -4,4'-dicarboxylic acid and other alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, phthalic acid, 1,4 / 1,5 / 2,6 / 2,7-naphthalenedicarboxylic acid, diphenylmethane-4,4 Examples include aromatic dicarboxylic acids such as alkali metal salts of 3-sulfoisophthalic acid such as' -dicarboxylic acid, sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate. These can use 1 type (s) or 2 or more types. Among these, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and alkali metal salt of 3-sulfoisophthalic acid are preferable, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and sodium 3-sulfoisophthalate are more preferable.

  The number average molecular weight of the polyamide hard segment (b1) is preferably 500 to 5000, and more preferably 500 to 3000. When the number average molecular weight is less than the above value, the heat resistance of the polyether ester amide elastomer itself may decrease. When the number average molecular weight exceeds the above value, the reactivity decreases, and thus the polyether ester amide elastomer (B2) is produced. It may take a lot of time.

The soft segment (b2) of the polyether ester amide elastomer (B2) is a polyalkylene oxide compound represented by the general formula (1).
Examples of the polyalkylene oxide compound represented by the general formula (1) include polyethylene oxide (polyethylene glycol) and polypropylene oxide (polypropylene glycol and polytetramethylene oxide. These may be used alone or in combination of two or more. For example, a compound in which Q in formula (1) contains 2 and 3 carbon atoms, a compound in which Q in formula (1) contains 2 and 4 carbon atoms, and Q in formula (1) Examples thereof include compounds containing 3 and 4 carbon atoms, and among these, ethylene oxide is preferable from the viewpoint of antistatic properties.

  The number average molecular weight of the soft segment (b2) of the polyetheresteramide elastomer (B2) is 300 to 5000, preferably 500 to 3000, and more preferably 1000 to 3000. When the number average molecular weight of the soft segment (b2) is less than the above value, the antistatic property becomes insufficient. When the number average molecular weight exceeds the above value, the reactivity decreases, and thus the polyether ester amide elastomer (B2) is greatly produced. Takes a lot of time.

  In the polyetheresteramide elastomer (B2), the content ratio of the soft segment (b2) is 20 to 80% by weight with respect to 100% by weight of the total weight of the polyamide hard segment (b1) and the soft segment (b2). Is preferable, and it is more preferable that it is 25 to 75 weight%. When the content of the soft segment (b2) is less than the above value, the antistatic property may be inferior, and when it exceeds the above value, the heat resistance may be deteriorated.

The production method of the polyether ester amide elastomer (B2) is not particularly limited.
Production method 1: A method in which a polyamide-forming unit and a dicarboxylic acid are reacted to form (b1), and (b2) is added thereto, and a polymerization reaction is performed at a high temperature and under reduced pressure.
Production method 2: Polyamide-forming unit, dicarboxylic acid and (b2) are charged into a reaction vessel at the same time, and an intermediate is produced by a pressure reaction at high temperature in the presence or absence of water, and then under reduced pressure (b1 ) And (b2) and the like.

  In the above polymerization reaction, a known esterification catalyst is usually used. Examples of the catalyst include antimony catalysts such as antimony trioxide, tin catalysts such as monobutyltin oxide, titanium catalysts such as tetrabutyl titanate, zirconium catalysts such as tetrabutyl zirconate, organic compounds such as zirconyl acetate and zinc acetate. Examples include acid metal salt catalysts. It is preferable that the usage-amount of a catalyst is 0.1-5 weight part with respect to the total amount of (b1) and (b2).

  The relative viscosity (0.5% by weight, m-cresol solution, 25 ° C.) of the polyetheresteramide elastomer (B2) is preferably 1.2 to 3.0, and preferably 1.3 to 2.5. It is more preferable. If the relative viscosity is less than the above value, heat resistance may be inferior, and if it exceeds the above value, moldability may be deteriorated.

The electrolyte salt compound (b3) of the polyether ester amide elastomer (B2) has almost no humidity dependency without reducing the bending fatigue resistance of the polyamide-laminated biaxially stretched film of the present invention, and has excellent antistatic performance. It is a component which can provide.
The electrolyte salt compound (b3) is a metal salt component composed of an alkali metal or alkaline earth metal cation and an anion capable of ion dissociation.
Examples of alkali metal ions include sodium, potassium, lithium, cesium and the like. Examples of alkaline earth metal ions include magnesium and calcium. These can use 1 type (s) or 2 or more types. Among these, sodium, potassium, and lithium having a small ionic radius are preferable, and sodium and lithium are more preferable.

Examples of the ion dissociable anion of the electrolyte salt compound (b3) include perhalogenate anions such as perchloric acid and perbromate, halogen anions such as chlorate and bromate, and halogen anions such as chlorine, bromine, fluorine and iodine. Alkyl sulfonate anions such as octyl sulfonate and stearyl sulfonate, aryl sulfonate anions such as dodecylbenzene sulfonate and benzene sulfonate, alkyl sulfate anions such as lauryl sulfate and ethyl sulfate, sulfate anions, acetic acid and propionic acid Carboxylic acid anion, alkyl phosphate anion, phosphate anion, phosphite anion, nitrate anion, carboxylic acid anion, halide anions such as tetrafluoroboron, hexafluoroarsenic, hexafluorophosphorus, trichloromethanesulfonic acid, trifluoromethanesulfuric acid Phosphate, bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane, trichloroacetic acid, an organic acid anion having a halogenated alkyl, such as trifluoroacetic acid, thiocyanate anions, tetraphenylboron anions and the like. These can use 1 type (s) or 2 or more types.
Among these, perchloric acid, trifluoromethanesulfonic acid, bis (trifluoromethanesulfonyl) imide and tris (trifluoromethanesulfonyl) methane anion are preferable, and perchlorate anion is more preferable.

Specific examples of the electrolyte salt compound (b3) include lithium perchlorate LiClO ₄ , sodium perchlorate NaClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoromethanesulfonyl) imide lithium Li · N (CF3SO _{2) 2,} bis (trifluoromethanesulfonyl) imide sodium _{Na · N (CF 3 SO 2} ) 2, tris (trifluoromethanesulfonyl) methane lithium _{Li · C (CF 3 SO 2} ) 3, tris (trifluoromethanesulfonyl) Methane sodium Na.C (CF ₃ SO ₂ ) ₃ may be mentioned. These can use 1 type (s) or 2 or more types. Among these, sodium perchlorate, lithium perchlorate, sodium trifluoromethanesulfonate, sodium bis (trifluoromethanesulfonyl) imide, and sodium tris (trifluoromethanesulfonyl) methane are more preferable, and sodium perchlorate is particularly preferable.

  As a method for adding the electrolyte salt compound (b3) to the polymer used for the polyether ester amide elastomer (B2), in order to effectively disperse it in the composition, it is pre-dispersed in the polyether ester amide elastomer (B2). In particular, it is desirable to add and disperse in advance during the production of the polyetheresteramide elastomer (B2). Here, in order to produce a polyamide elastomer in the presence of the electrolyte salt compound (b3), the electrolyte salt compound is batched or divided before polymerization of the elastomer, during polymerization, or after separation and recovery of the elastomer after polymerization. Can be added. Moreover, as an addition method of this electrolyte salt compound (b3), you may add as it is, may melt | dissolve in a polymerization component previously, may add, and also melt | dissolve and add in another solvent.

  The amount of the electrolyte salt compound (b3) used is 0.01 to 10% by weight with respect to the total amount of (b1) and (b2) in the (B2) polyether ester amide elastomer, and 0.02 to 5%. % By weight is preferable, and 0.05 to 3% by weight is more preferable. When the amount of the electrolyte salt compound (b3) used is less than the above value, the antistatic performance is inferior, whereas when it exceeds the above value, the surface appearance of the film is inferior. In particular, it is necessary to pay attention to the number of moles of alkali metal or alkaline earth metal cations in the electrolyte salt compound (b3) with respect to the number of moles of polyalkylene oxide of the soft segment (b2) in the polyetheresteramide elastomer (B2). is there. It is desirable that the number of moles of alkali metal or alkaline earth metal cation in the electrolyte salt compound (b3) with respect to the polyalkylene oxide of the soft segment (b2) be equal to or lower than the saturated dissolution concentration. When the concentration is higher than the saturated dissolution concentration, the electrolyte salt compound (b3) component not dissolved in the polyalkylene oxide of the soft segment (b2) does not contribute to the antistatic effect.

  In the aliphatic polyamide resin composition (B), the blending ratio of the aliphatic polyamide (B1) and the polyether ester amide elastomer (B2) is the sum of the aliphatic polyamide (B1) component and the polyether ester amide elastomer (B2) component. Based on the amount (100% by weight), the aliphatic polyamide (B1) component is in the range of 70 to 99.5% by weight and the polyetheresteramide elastomer (B2) component is in the range of 30 to 0.5% by weight. The component (B1) is preferably 75 to 98% by weight and the polyether ester amide elastomer (B2) component is preferably 25 to 2% by weight. When the blending ratio of the polyetheresteramide elastomer (B2) component is less than the above values, the effect of improving the antistatic property and the bending fatigue resistance is small. The performance deteriorates, and an improvement in the effect cannot be expected, which is economically disadvantageous.

  In the aliphatic polyamide resin composition (B), the blending method of the aliphatic polyamide (B1) and the polyether ester amide elastomer (B2) is necessary for the aliphatic polyamide (B1) and the polyether ester amide elastomer (B2). According to the method, various additives are blended and mixed by a known method. For example, using a tumbler or mixer, a dry blend method in which a polyamide resin raw material is directly added at the time of molding, and kneading by kneading the polyamide resin raw material in advance using a uniaxial or biaxial extruder at a concentration used during molding. Or a master batch method in which a polyamide-based resin raw material is kneaded in advance at a high concentration using a uniaxial or biaxial extruder and diluted at the time of molding.

The layer (c) is a layer containing the semi-aromatic polyamide (A) and the aliphatic polyamide resin composition (B), and may be a mixture of virgin raw materials, or the polyamide of the present invention. Non-standard film produced when producing a laminated biaxially stretched film, a scrap mixture generated as a cut end material (ear trim) at the film side end, or a virgin raw material added to the scrap mixture. There may be.
In the layer (c), the mixing ratio of the semi-aromatic polyamide (A) and the aliphatic polyamide resin composition (B) is not particularly limited, but the weight ratio of (A) and (B) is 7: 3- It is preferable to select within the range of 1: 9. These mixing can be performed by a well-known method, mix | blending various additives as needed. Using a known mixing device such as a tumbler or mixer, a method of uniformly dry-blending each polymer pellet so that the mixing ratio is as described above, and a concentration at which each polymer pellet is used at the time of molding Examples thereof include a kneading method in which dry blending is performed in advance, and melt kneading and mixing is performed using a single screw or twin screw extruder.

  Furthermore, the semi-aromatic polyamide (A) and the aliphatic polyamide resin composition (B) have a water extraction amount of 1% or less measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920. It is preferable that it is 0.5% or less. When the amount of water extraction exceeds the above-mentioned value, the oligomer component is remarkably adhered to the vicinity of the die, and appearance defects may easily occur due to the generation of die lines and fish eyes due to these deposits. Furthermore, the semi-aromatic polyamide (A) and / or the aliphatic polyamide resin composition (B) has a high hygroscopic property, and when a hygroscopic material is used, an oligomer is generated because hydrolysis occurs when the raw material is melt-extruded. And since film manufacture becomes difficult, it is preferable to dry in advance and to have a moisture content of 0.1% by weight or less.

  In the semi-aromatic polyamide (A) and / or the aliphatic polyamide resin composition (B), an antioxidant, a heat stabilizer, a weathering agent, a lubricant, an inorganic fine particle, as long as the properties of the obtained film are not impaired. You may mix | blend an antistatic agent, an antiblocking agent, an antifogging agent, a coloring agent, another thermoplastic resin, etc.

  The polyamide laminated biaxially stretched film according to the present invention includes a (a) layer containing a semi-aromatic polyamide (A), a (b) layer containing an aliphatic polyamide resin composition (B), a semi-aromatic polyamide (A), Lamination of at least two layers obtained by laminating (a) layer and at least one layer selected from (b) layer and (c) layer among (c) layer containing aliphatic polyamide resin composition (B) It is a stretched film obtained by biaxially stretching a film, and a biaxially stretched film obtained by biaxially stretching at least three laminated films in which both outer layers are selected from the (b) layer and the (c) layer.

Specific examples of the layer structure of the polyamide laminated biaxially stretched film are as follows:
1) In the case of a two-layer structure, (a) / (c), (a) / (b),
2) In the case of a three-layer structure, (a) / (b) / (c), (b) / (c) / (a), (b) / (a) / (b), (c) / (a ) / (C), (b) / (a) / (c),
3) In the case of a four-layer structure, (b) / (c) / (a) / (b), (b) / (c) / (a) / (c), (c) / (b) / (a ) / (C), (c) / (b) / (a) / (c), etc.
4) In the case of a five-layer structure, (b) / (c) / (a) / (c) / (b), (c) / (b) / (a) / (b) / (c), (b ) / (A) / (c) / (a) / (b), (c) / (a) / (b) / (a) / (c), etc., but are limited to those exemplified. It is not something.
Considering the achievement degree of the present invention and the ease of production, it is preferably 3 layers or more, and more preferably 3 to 5 layers. Moreover, when manufacturing a laminated film, a non-standard film and a cut end material (ear trim) are generated. When these are used and considering economical efficiency and effective use of resources, (c) / (a) / ( c) and (b) / (a) / (c), and (b) / (c) / (a) / (c) / (b) are preferred. (B) / (a) / (b) is preferable.

The polyamide laminated biaxially stretched film according to the present invention can be produced by a known method. For example, it can be produced by a so-called coextrusion method such as coextrusion sheet molding, coextrusion casting film molding, and coextrusion blown film molding.
First, using a semi-aromatic polyamide (A), an aliphatic polyamide resin composition (B), a mixture (C) of a semi-aromatic polyamide (A) and an aliphatic polyamide resin composition (B), A non-stretched laminated film which is amorphous and not oriented is manufactured by a method such as a coextrusion method. For example, a resin raw material melted in a separate extruder is continuously extruded from a T-die, and co-extruded T-die method in which it is formed into a film while cooling with a casting roll, continuously extruded from an annular die, A co-extrusion water-cooled inflation method in which water is brought into contact and cooling, a co-extrusion air-cooled inflation method in which extrusion is performed from an annular die, and cooling is performed by air can be used. At this time, if necessary, an adhesive layer can be provided between each of the layers (a), (b) and / or (c), and a maleic anhydride-modified polyolefin as a resin component of the adhesive layer, An ethylene / (meth) acrylic acid copolymer, an ionomer resin, or the like can be used.

  As a method for forming a raw film for a stretched film, the coextrusion T-die method and the coextrusion water-cooled inflation method are particularly excellent in terms of continuous stretchability. Further, the obtained unstretched laminated film is stretched. A known method can be applied to the stretching method. Specifically, (1) a sequential biaxial stretching method in which an unstretched sheet melt-extruded from a T-die is stretched in the longitudinal direction with a roll-type stretching machine and then stretched in the transverse direction with a tenter-type stretching machine; The stretched sheet can be produced by a simultaneous biaxial stretching method in the longitudinal and lateral directions simultaneously with a tenter type simultaneous biaxial stretching machine, or (3) a tubular stretching method in which a sheet melt-extruded into a tube shape is stretched in an inflation type with a gas pressure.

  Next, the unstretched laminated film is preferably biaxially stretched in the range of 2.0 to 5.0 times in the film flow direction (longitudinal direction) and in the direction perpendicular to the film flow direction (transverse direction). When the draw ratio is less than the above value, the effect of improving the operation stability (stretchability) does not appear remarkably, and the strength and barrier properties of the resulting film may be inferior. Moreover, when a draw ratio exceeds the said value, a film may tear at the time of extending | stretching, or may fracture | rupture. It is preferable that the draw ratio of each length and width is 2.5 to 4.0 times.

  For example, in the tenter-type sequential biaxial stretching method, the laminated unstretched film is heated to a temperature range of 40 to 120 ° C., stretched in the machine direction by a roll-type longitudinal stretching machine, and subsequently 60-180 by a tenter-type lateral stretching machine. The polyamide laminated biaxially stretched film of the present invention can be produced by stretching in the transverse direction within a temperature range of ° C. More preferably, the stretching temperature in the longitudinal direction is 70 to 100 ° C, and the stretching temperature in the transverse direction is 80 to 160 ° C.

The polyamide laminated biaxially stretched film stretched by the above method is subsequently heat treated. Dimensional stability at room temperature can be imparted by heat treatment. In this case, the heat treatment temperature is preferably selected within the range of 80 ° C. as the lower limit and the upper limit of the temperature 5 ° C. lower than the melting point of the (B) aliphatic polyamide resin composition. A stretched film having an arbitrary heat shrinkage rate can be obtained.
The coextruded laminated biaxially stretched film of the present invention desirably has poor heat shrinkage or substantially does not have it. Therefore, the heat treatment temperature performed after stretching is preferably 150 ° C. or higher, and more preferably 180 to 220 ° C. The relaxation rate is preferably within 20% in the width direction, and more preferably 3 to 10%.
The polyamide laminated biaxially stretched film sufficiently heat-set by the heat treatment operation is cooled and wound up according to a conventional method.

  The thickness of the polyamide laminated biaxially stretched film of the present invention is preferably 5 to 50 μm, more preferably 10 to 40 μm, and further preferably 10 to 30 μm. When the overall thickness is less than the above value, the balance between gas barrier properties and bending fatigue resistance may be deteriorated, and when it exceeds the above value, the film may be hardened, and further laminated In some cases, the entire film becomes very thick and is not suitable for flexible packaging.

  Furthermore, the polyamide laminated biaxially stretched film of the present invention can be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc. in order to enhance printability, lamination, and adhesive application. Moreover, after performing such a process as needed, it can be used for each intended use through secondary processing steps such as printing, laminating, adhesive application, heat sealing, and vapor deposition.

  The polyamide laminated biaxially stretched film of the present invention is excellent in gas barrier properties and transparency, and has a high utility value alone. However, in order to give a further function or to obtain an economically advantageous laminated film, A base material layer made of a plastic resin can be provided in the polyamide laminated biaxially stretched film of the present invention or outside the polyamide laminated biaxially stretched film of the present invention.

  Other thermoplastic resins include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLPDE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP ), Ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl acetate copolymer saponified product (EVOH), ethylene / acrylic acid Copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer Polyolefin resins such as (EEA) and acrylic acid, methacrylic , Maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2,2,1] -5-heptene- Carboxyl groups such as 2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] -5 -An acid anhydride group such as heptene-2,3-dicarboxylic acid anhydride, a functional group such as an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, Polyolefin resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyester Polyethylene resins such as lenisophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystal polyester (LCP), polyacetal (POM) Polyether resins such as polyphenylene oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polythioether resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES), Polyketone resins such as polyetheretherketone (PEEK) and polyallyletherketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylate Polynitrile resins such as rilonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethyl methacrylate (PMMA), polyethyl methacrylate Polymethacrylate resins such as (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymers, vinylidene chloride / methyl Polyvinyl chloride resins such as acrylate copolymers, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (PI), polyamideimide (PAI), polyether imi Polyimide resins such as polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / Examples thereof include fluorine resins such as fluoro (alkyl vinyl ether) copolymers (PFA), thermoplastic polyurethane resins, polyurethane elastomers, polyester elastomers, polyamide elastomers, and the like.

  The polyamide laminated biaxially stretched film can be provided with a sealant layer on the outside of the polyamide laminated biaxially stretched film of the present invention or the polyamide laminated biaxially stretched film of the present invention. The sealant layer may be any resin that can be heat-sealed, and generally includes a polyolefin-based polymer, polyester, and the like. Specifically, polypropylene (PP), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / Methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), ionomer resin, amorphous Although polyester (A-PET) etc. are mentioned, it is not limited to these.

  As for the thickness of a sealant layer, about 15-80 micrometers is common. If the thickness of the sealant layer is less than the above value, the adhesive strength tends to be inferior. On the other hand, if the thickness exceeds the above value, it tends to be unsuitable for flexible packaging applications. As a method for laminating the sealant layer, a general method such as extrusion laminating and dry laminating, or a combination thereof is adopted, but the method is not limited thereto. When laminating, it is preferable to use one or both sides of a polyamide laminated biaxially stretched film after corona treatment.

For example, in the case of extrusion lamination, an anchor coat agent is applied to the polyamide laminated biaxially stretched film of the present invention and a base material such as a thermoplastic resin, and after drying, a thermoplastic resin such as a polyethylene resin is interposed therebetween. A laminated film is obtained by cooling between rolls while melt extrusion and applying pressure under pressure.
In the case of dry lamination, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound is applied to the polyamide laminated biaxially stretched film of the present invention, and after drying, a substrate such as a thermoplastic resin A laminated film is obtained by pasting together. The film after lamination can be increased in adhesive strength by aging.

  The polyamide laminated biaxially stretched film of the present invention is the polyamide laminated biaxially stretched film of the present invention, or a paper, metal foil, or woven fabric that is a substrate other than a thermoplastic resin outside the polyamide laminated biaxially stretched film of the present invention. It can be used by laminating non-woven fabric, metallic cotton, wood and the like.

  The polyamide laminated biaxially stretched film of the present invention is useful as a packaging material that seals foods, pharmaceuticals, medicines, fragrances, etc. whose contents are not subject to alteration by oxygen. , Pouches, vacuum packaging, skin packs, deep drawing packaging, rocket packaging. The pouches can be used for three-side seals, four-side seals, pillows, gussets, standing pouches, and the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
In addition, the evaluation method of the material used in the following Examples and Comparative Examples and various films is shown.

[Materials Used in Examples and Comparative Examples]
1) Semi-aromatic polyamide (A)
(A-1): Polymetaxylylene adipamide (Mitsubishi Gas Chemical Company, MX-nylon 6011)

2) Aliphatic polyamide (B1)
(B1-1): Polyamide 6 (Ube Industries, UBE NYLON 1022BF, relative viscosity 3.35) (B2-2): Polyamide 12 (Ube Industries, UBESTA3030XA, relative viscosity 2.24)
3) Polyetheresteramide elastomer (B2)
(B2-1): Polyether ester amide elastomer (manufactured by Ciba Specialty Chemicals, polyether ester amide elastomer containing irgastat P22, caprolactam, adipic acid, polyethylene oxide and sodium perchlorate)
(B2-2): Polyetheresteramide elastomer (manufactured by Ciba Specialty Chemicals, polyetheresteramide elastomer containing irgastat P18, dodecane lactam, adipic acid, polyethylene oxide and sodium perchlorate)
(B2-3): Polyether ester amide elastomer (manufactured by Daicel Degussa, polyether amide amide elastomer comprising diamide E40-S3, dodecane lactam, dodecadicarboxylic acid, polytetramethylene oxide)

4) Mixture (C)
(C-1): Ear trim end material generated from film production test (40% by weight of semi-aromatic polyamide (A-1), 56% by weight of aliphatic polyamide (B1-1), polyether ester amide elastomer (B2) -1) Mixture with 4% by weight)
(C-2): Resin composition in which 55% by weight of aliphatic polyamide resin composition (B-1) and 45% by weight of mixture (C-1) were blended (semi-aromatic polyamide (A-1) 18% by weight) , A mixture of aliphatic polyamide (B1-1) 73.8% by weight and polyetheresteramide elastomer (B2-1) 8.2% by weight), but the aliphatic polyamide resin composition (B-1) A mixture of 90% by weight of an aromatic polyamide (B1-1) and 10% by weight of a polyetheresteramide elastomer (B2-1)

5) Polyolefin (D-1): Adhesive polyolefin (manufactured by Mitsui Chemicals, Admer NF528).
(D-2): Ethylene / ethyl acrylate copolymer (EEA) (Mitsui / DuPont Polychemicals, Evaflex A703).

[Evaluation of transparency]
The haze was measured using a direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP) according to ASTM D-1003.

[Evaluation of oxygen permeability]
In accordance with ASTM D-3985, measurement was performed under conditions of 23 ° C. and 50% relative humidity using an oxygen gas permeation measuring device (MOCON-OX-TRAN 2/20, manufactured by Modern Control Co., Ltd.).

[Evaluation of bending fatigue resistance]
A film cut to a size of 8 inches × 11 inches is conditioned for 24 hours at 23 ° C. and a relative humidity of 65%, and a gelbo flex tester (manufactured by Rigaku Corporation) is used. The number of pinholes produced after 1000 bending tests at 23 ° C. was measured by a method based on MIL-B-131C.

[Evaluation of antistatic properties]
(1) Surface resistivity: After conditioning the film for 3 days at 23 ° C. and 50% relative humidity, using an insulation resistance meter (Yokogawa Hewlett-Packard, Model 4329A), 23 ° C. and 50% relative humidity Then, the surface resistivity was measured under the conditions of an applied voltage of 500 V and 30 seconds.
(2) Electrostatic half-life: After conditioning the film for 3 days at 23 ° C. and 60% relative humidity, using a static Honest meter (H-0110, manufactured by Sisid Electrostatic Co., Ltd.), 23 ° C. and 50% relative humidity In the atmosphere, the charged voltage half-life was measured under the conditions of applied voltage of 10 kV and distance between samples of 20 mm.

Example 1
A blend of 90 parts by weight of an aliphatic polyamide (B1-1) and 10 parts by weight of a polyetheresteramide elastomer (B2-1) is supplied to a twin-screw extruder (manufactured by Nippon Steel Works, TEX30 type). The mixture was melt-kneaded under the conditions of a preset temperature of 250 ° C. and a screw rotation speed of 100 rpm, granulated and dried to obtain an aliphatic polyamide resin composition (B-1).
Using a semi-aromatic polyamide (A-1) for the layer (a) and the aliphatic polyamide resin composition (B-1) for the layer (b), in a 40 mmφ extruder equipped with a circular three-layer die The resin component of the layer (a) was melted separately at an extrusion temperature of 280 ° C., and the resin component of the layer (b) was melted separately at an extrusion temperature of 260 ° C. A polyamide-laminated unstretched film was obtained by directly laminating three layers of b) / (a) / (b) that were substantially amorphous and not oriented.
Subsequently, stretching was performed at a stretching temperature of 180 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. Then, the end of the tubular film was cut open, the flat film was introduced into the tenter, and heat-fixed at 210 ° C. while performing relaxation treatment in the width direction. Both ends of the film were released from the clip, and the ears were trimmed and wound to obtain a polyamide laminated biaxially stretched film having (b) / (a) / (b) of 5 μm / 5 μm / 5 μm. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

(Example 2)
Instead of the aliphatic polyamide resin composition (B-1) of Example 1, 95 parts by weight of aliphatic polyamide (B1-1) and polyether ester amide elastomer (B2-1) were prepared in the same manner as in Example 1. ) 5 parts by weight of an aliphatic polyamide resin composition (B-2) was obtained. (B) A polyamide laminated biaxially stretched film was obtained in the same manner as in Example 1, except that the aliphatic polyamide resin composition (B-2) was used for the layer. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

(Example 3)
A blend of 90 parts by weight of an aliphatic polyamide (B1-2) and 10 parts by weight of a polyetheresteramide elastomer (B2-2) is supplied to a twin-screw extruder (manufactured by Nippon Steel Co., Ltd., TEX30 type). The mixture was melt-kneaded under the conditions of a preset temperature of 240 ° C. and a screw rotation speed of 100 rpm, granulated and dried to obtain an aliphatic polyamide resin composition (B-3).
(A) The semi-aromatic polyamide (A-1) is used for the layer, the aliphatic polyamide resin composition (B-3) is used for the (b) layer, and the polyolefin (D-1) is used for the (d) layer, In a 40 mmφ extruder equipped with a circular five-layer die, the resin component of (a) layer was extrusion temperature of 280 ° C., the resin component of layer (b) was extrusion temperature of 250 ° C., and the resin component of layer (d) was extrusion temperature. It is melted separately at 190 ° C., taken up while being cooled with water at 20 ° C., and the layer structure is substantially amorphous (b) / (d) / (a) / (d) / (b) A polyamide-laminated unstretched film having 5 adhesive layers that were not oriented was obtained. Subsequently, stretching was performed at a stretching temperature of 170 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. Then, the end of the tubular film was cut open, the flat film was introduced into the tenter, and a heat setting treatment was performed at 180 ° C. while performing a relaxation treatment in the width direction. Both ends of the film are released from the clip, and the ears are trimmed and wound up. (B) / (d) / (a) / (d) / (b) = 3 μm / 2 μm / 5 μm / 2 μm / 3 μm (total thickness 15 μm ) Was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

Example 4
Using the semi-aromatic polyamide (A-1) for the layer (a), the aliphatic polyamide resin composition (B-1) for the layer (b), and the mixture (C-1) for the layer (c), In a 40 mmφ extruder equipped with a circular three-layer die, the resin component of (a) layer was extrusion temperature of 280 ° C., the resin component of layer (b) was extrusion temperature of 260 ° C., and the resin component of layer (c) was extrusion temperature. It is melted separately at 280 ° C. and taken up while being cooled with water at 20 ° C., and the layer structure is substantially amorphous (b) / (a) / (c) and not oriented (b) A polyamide laminated unstretched film obtained by directly laminating three layers in the order of layer, (a) layer and (c) layer was obtained. Subsequently, stretching was performed at a stretching temperature of 180 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. Then, the end of the tubular film was cut open, the flat film was introduced into the tenter, and heat-fixed at 210 ° C. while performing relaxation treatment in the width direction. Both ends of the film were released from the clip, and the ears were trimmed and wound to obtain a polyamide laminated biaxially stretched film of (b) / (a) / (c) = 6 μm / 4 μm / 5 μm. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

(Example 5)
Using the semi-aromatic polyamide (A-1) for the layer (a) and the mixture (C-2) for the layer (c), in a 40 mmφ extruder equipped with a circular three-layer die, the layer (a) The resin component of (c) was melted separately at an extrusion temperature of 280 ° C. and the resin component of the layer (c) was melted separately at an extrusion temperature of 270 ° C. ) / (C) A substantially non-oriented and unoriented (c) layer and (a) layer were directly laminated in three layers to obtain a polyamide laminated unstretched film. Subsequently, stretching was performed at a stretching temperature of 180 ° C. and a stretching ratio (both longitudinal and lateral) of 3.0 times by a tubular stretching method in which a longitudinal and lateral stretching was simultaneously performed in an inflation type with a gas pressure. Then, the end of the tubular film was cut open, the flat film was introduced into the tenter, and heat-fixed at 210 ° C. while performing relaxation treatment in the width direction. Both ends of the film were released from the clip, and the ears were trimmed and wound to obtain a polyamide laminated biaxially stretched film of (b) / (a) / (c) = 5.5 μm / 4 μm / 5.5 μm. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

(Comparative Example 1)
Polyamide laminated biaxial stretching in the same manner as in Example 1 except that polyamide (B1-1) was used instead of the polyamide resin composition (B-1) as the resin component of the layer (b) in Example 1. A film was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.

(Comparative Example 2)
In Example 1, the polyamide laminate was formed in the same manner as in Example 1 except that the polyamide resin composition (B-4) was used instead of the polyamide resin composition (B-1) as the resin component of the layer (b). A biaxially stretched film was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.
However, the polyamide resin composition (B-4) was prepared by blending 99 parts by weight of aliphatic polyamide (B1-1) and 1 part by weight of a polyetheresteramide elastomer (B2-1). (TEX30 type, manufactured by Tosho Co., Ltd.), melt kneaded, granulated and dried under conditions of an extruder set temperature of 240 ° C. and a screw rotation speed of 100 rpm.

(Comparative Example 3)
In Example 1, the polyamide laminate was formed in the same manner as in Example 1 except that the polyamide resin composition (B-5) was used instead of the polyamide resin composition (B-1) as the resin component of the layer (b). A biaxially stretched film was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.
However, the polyamide resin composition (B-5) was prepared by blending 60 parts by weight of an aliphatic polyamide (B1-1) and 40 parts by weight of a polyetheresteramide elastomer (B2-1). (TEX30 type, manufactured by Tosho Co., Ltd.), melt kneaded, granulated and dried under conditions of an extruder set temperature of 240 ° C. and a screw rotation speed of 100 rpm.

(Comparative Example 4)
Polyamide laminated biaxial stretching in the same manner as in Example 1 except that the polyamide resin composition (B-6) was used instead of the polyamide resin composition (B-1) as the resin component of the layer (b) in Example 1. A film was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.
However, the polyamide resin composition (B-6) was prepared by blending 90 parts by weight of an aliphatic polyamide (B1-1) and 10 parts by weight of a polyetheresteramide elastomer (B2-3). (TEX30 type, manufactured by Tosho Co., Ltd.), melt kneaded, granulated and dried under conditions of an extruder set temperature of 240 ° C. and a screw rotation speed of 100 rpm.

(Comparative Example 5)
In Example 1, the polyamide laminate was formed in the same manner as in Example 1 except that the polyamide resin composition (B-7) was used instead of the polyamide resin composition (B-1) as the resin component of the layer (b). A biaxially stretched film was obtained. The physical property measurement results of the polyamide laminated biaxially stretched film are shown in Table 1.
However, the polyamide resin composition (B-7) was prepared by blending 97 parts by weight of aliphatic polyamide (B1-1) and 3 parts by weight of polyolefin (D-2) with a twin-screw extruder (manufactured by Nippon Steel Works, TEX30 type), melt kneaded, granulated and dried under conditions of an extruder set temperature of 240 ° C. and a screw rotation speed of 100 rpm.

The polyamide-laminated biaxially stretched film of the present invention has gas barrier properties, flex fatigue resistance, transparency, powder and dust hardly adhere electrostatically, has low humidity dependency, and has long-lasting antistatic properties. Therefore, each performance balance is optimized.

Claims (4)

A polyamide laminate characterized by biaxially stretching a laminated film of at least two layers obtained by laminating the following (a) layer and at least one layer selected from the following (b) layer and the following (c) layer: Biaxially stretched film.
(A) Layer: 70 mol% or more of a polyamide constituent unit derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 12 carbon atoms in the molecular chain The layer containing the semi-aromatic polyamide (A) to contain.
(B) Layer: A layer comprising an aliphatic polyamide resin composition (B) comprising 70 to 98% by weight of aliphatic polyamide (B1) and 30 to 2% by weight of the following polyetheresteramide elastomer (B2).
(B) Polyether ester amide elastomer (B2) of the layer: containing 60% by weight or more of the same polyamide forming unit as the aliphatic polyamide (B1), among aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid A polyamide hard segment (b1) comprising at least one dicarboxylic acid selected from:
A soft segment (b2) comprising a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5,000;
A polyetheresteramide elastomer comprising an electrolyte salt compound (b3),
A polyether ester amide elastomer containing 0.01 to 10% by weight of (b3) with respect to the total weight (100% by weight) of (b1) and (b2).

(In the formula, Q represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 50.)
(C) Layer: A layer containing a semi-aromatic polyamide (A) and an aliphatic polyamide resin composition (B).   The aliphatic polyamide (B1) is a homopolymer composed of at least one polyamide-forming unit selected from the group consisting of caprolactam, dodecane lactam, 12-aminododecanoic acid and hexamethylenediamine-adipate, or a copolymer thereof. The polyamide laminated biaxially stretched film according to claim 1, wherein The dicarboxylic acid of the polyamide hard segment (b1) of the polyetheresteramide elastomer (B2) is at least one dicarboxylic acid selected from the group consisting of adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate. Yes,
The polyamide-laminated biaxially stretched film according to claim 1 or 2, wherein the polyalkylene oxide of the soft segment (b2) is an alkylene group having a Q of 2 and / or 3 in the general formula (1). . The polyamide laminated biaxially stretched film is a layer in which both outer layers are selected from the (b) layer and the (c) layer, and is at least three layers. Polyamide laminated biaxially stretched film.