JP2006037070A - Polyamide resin composition and molded product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the humidity dependence of antistatic properties for preventing various troubles caused by static electricity, to be excellent in slipperiness under high humidity, to maintain its effect over a long period of time, and at low temperature An object of the present invention is to provide a polyamide resin composition that is capable of producing molded articles such as a polyamide film and a biaxially stretched polyamide film that have excellent pinhole resistance and retain the original transparency of the polyamide film.
A polyamide resin composition comprising a polyamide composition (A), an inorganic filler (B) and a bisamide compound (C),
(I) Polyamide composition (A) contains 70-99.5 wt% of polyamide resin (D) and 30-0.5 wt% of polyamide elastomer composition (E),
(II) A polyamide resin composition (E) contains 99.99% by weight of a polyamide elastomer (F) and 0.01 to 10% by weight of an electrolyte salt compound.
[Selection figure] None

Description

  The present invention is a polyamide film and a stretched polyamide film that are less dependent on humidity, have antistatic properties that last for a long time, have excellent slipperiness under high humidity, and have excellent transparency and pinhole resistance. The present invention relates to a polyamide resin composition from which a product can be obtained, a polyamide film and a stretched polyamide film produced from the polyamide resin composition, and a laminated film of these films.

Polyamide film is used in a wide range of fields because of its excellent mechanical properties, thermal properties, barrier properties, as well as impact resistance, wear resistance, and pinhole resistance, which are regarded as important in the packaging material field. ing.
However, since the polyamide film has a high electrical resistivity and is easily charged, the charged electricity cannot be leaked, and dust adheres to the surface or various troubles due to static electricity occur.
As a method for improving these drawbacks, a method is known in which a surface active agent or the like is applied to the surface, or a water-absorbing compound such as polyalkylene oxide or a low molecular weight antistatic agent such as alkylamine is kneaded into a resin. However, antistatic agents such as surfactants, polyalkylene oxides, and alkylamines are excellent in initial antistatic properties, 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.

  Patent Documents 1 and 2 propose a method of blending a polyether ester amide elastomer mainly composed of polyamide and polyoxyalkylene glycol with a thermoplastic resin as a method for improving the sustainability of the antistatic effect. .

On the other hand, when the polyamide film is in close contact with the contents, it has a higher elastic modulus and is harder than the polyolefin-based film, so the followability to the surface shape of the contents is poor, and the contents in the film folding part (bending part) There is a problem that pinholes are likely to be generated due to friction with the material.
Furthermore, due to recent development of freezing technology, it is often handled in a low temperature atmosphere of 5 ° C. or less after food packaging. Among these properties, pinhole resistance and flexibility, which are the most important in practice, are markedly temperature-dependent. When used in a low temperature atmosphere of 5 ° C or less, the leakage of the filler due to pinholes Troubles such as the above occurred, and it was not always satisfactory in practical use. As an improvement method for enabling use of the polyamide film in a low temperature atmosphere of 5 ° C. or less, Patent Document 3 discloses a polyamide film comprising a polyamide and a polyether ester amide elastomer using polyoxytetramethylene glycol as a polyether component. Is disclosed.

  Patent Document 4 discloses (A) 70-99.5% by weight of a polyamide resin and (B) (a) at least one polyamide selected from the group consisting of lactam, aminocarboxylic acid, and a salt of diamine and dicarboxylic acid. A forming unit, a polyamide hard segment composed of at least one dicarboxylic acid selected from aliphatic dicarboxylic acid, alicyclic dicarboxylic acid and aromatic dicarboxylic acid, and (b) an aromatic having a specific structure having a number average molecular weight of 300 to 5,000. A soft segment comprising a ring-containing polyether, and (c) an alkali metal and / or alkaline earth metal compound, and (c) is 0.01 to 5 with respect to the total weight of (a) and (b) Polyamide composed of a polyamide composition (A) containing 30 to 0.5% by weight of a polyetheresteramide elastomer contained by weight% Film is disclosed.

Japanese Patent Application Laid-Open No. 60-23435 JP-A-60-170646 JP-A-5-230365 JP 2003-012921 A

  Known methods for improving the slipperiness of the polyamide film include a method of forming protrusions on the film surface by adding an inorganic filler such as silica and kaolin, and a method of adding an organic lubricant such as a bisamide compound. The method of forming surface protrusions by adding an inorganic filler has a problem that when the amount added is large, the transparency of the film is lowered and the commercial value is lost as a packaging film. When the amount of the organic lubricant added is large, the adhesion of the printing ink at the time of printing of the film is reduced and printing failure occurs, the adhesion with the adhesive at the time of lamination is reduced, and delamination is caused. appear. In order to improve slipperiness under high humidity, it has been proposed to use an inorganic filler and an organic lubricant in combination, but it is difficult to optimize the balance between transparency and slipperiness. Furthermore, the high-performance polyamide film that balances excellent antistatic properties, transparency, and slipperiness at high temperatures at a high level is actually not obtained industrially, and its development is desired. By the way.

The present invention has less anti-static humidity dependency that prevents various troubles caused by static electricity, is excellent in slipperiness under high humidity, maintains its effect over a long period of time, and is resistant to low temperatures. An object of the present invention is to provide a polyamide resin composition capable of producing a molded product such as a polyamide film and a biaxially stretched polyamide film having excellent pinhole properties and maintaining the original transparency of the polyamide film.
In particular, an object of the present invention is to provide a resin composition capable of providing a fully aliphatic polyamide film and a molded product such as this film.

  As a result of intensive studies aimed at developing a molded product such as a polyamide film that solves the above-mentioned problems, the present inventors have blended a polyamide resin, a polyetheresteramide elastomer and an electrolyte compound, and further an inorganic filler and a bisamide compound. The inventors have found that a polyamide film obtained from the composition and a molded product such as a stretched film thereof are excellent in antistatic property, slipperiness under high humidity, pinhole resistance and transparency, and have reached the present invention.

The first of the present invention is a polyamide composition (A) 100 parts by weight,
A polyamide resin composition containing 0.1 to 1 part by weight of an inorganic filler (B) and 0.03 to 0.3 part by weight of a bisamide compound (C),
(I) Polyamide composition (A) contains 70-99.5 wt% of polyamide resin (D) and 30-0.5 wt% of polyamide elastomer composition (E),
(II) The polyamide elastomer composition (E) contains 99.99 to 90% by weight of the polyamide elastomer (F) and 0.01 to 10% by weight of the electrolyte salt compound,
(III) The polyamide elastomer (F) is a polyether ester amide obtained from a polyamide hard segment (a) and a soft segment (b) containing a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5000 An elastomer,
(IV) The polyamide hard segment (a) of the polyamide elastomer (F) contains 60% by weight or more of the same polyamide forming unit as the polyamide resin (D) with respect to 100% by weight of the polyamide hard segment (a), and is aliphatic. An object of the present invention is to provide a polyamide resin composition which is a polyamide hard segment (a) containing at least one dicarboxylic acid selected from dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids.

（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 second of the present invention is to provide a polyamide molded product obtained from the above polyamide resin composition.
The polyamide molded product is preferably a film or a stretched film.

Preferred embodiments of the first polyamide resin composition of the present invention and the second molded product of the present invention are shown below. In the present invention, a plurality of the following preferred embodiments can be combined.
In the first of the present invention and / or the second of the present invention, the polyamide resin (D) is selected from the group consisting of ε-caprolactam, ω-dodecanactam, 12-aminododecanoic acid, hexamethylenediamine adipate. A homopolymer or copolymer comprising at least one polyamide-forming unit is preferred.
In the first of the present invention and / or the second of the present invention, the polyamide elastomer (F) is:
(1) Polyamide hard segment (a) containing 60% by weight or more of the same polyamide-forming unit as the polyamide resin (D) with respect to 100% by weight, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid and 3-sulfoisophthalic acid A polyamide hard segment (a) containing at least one dicarboxylic acid selected from the group consisting of sodium,
And (2) a polyetheresteramide elastomer obtained from a soft segment (b) containing a polyalkylene oxide represented by the following general formula (2) having a number average molecular weight of 300 to 5,000.

（式中、Ｒは炭素数２〜３のアルキレン基、ｎは１〜５０の整数を表す。）
本発明の第一及び／又は本発明の第二では、無機フィラー（Ｂ）は、シリカ、カオリン及びタルクからなる群より選ばれる少なくとも一種を含むことが好ましい。
本発明の第一及び／又は本発明の第二では、ビスアミド化合物（Ｃ）は、エチレンビスステアリン酸アミド、エチレンビスベヘン酸アミド、エチレンビスオレイン酸アミド及びエチレンビスエルカ酸アミドからなる群より選ばれる少なくとも一種を含むことが好ましい。

(In the formula, R represents an alkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50.)
In the first of the present invention and / or the second of the present invention, the inorganic filler (B) preferably contains at least one selected from the group consisting of silica, kaolin and talc.
In the first and / or second of the present invention, the bisamide compound (C) is selected from the group consisting of ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide and ethylene bis erucic acid amide. It is preferable to include at least one kind.

The polyamide film and stretched polyamide film of the present invention can be laminated with other thermoplastic resin layers excluding the polyamide film of the present invention to provide a laminate film of at least two layers.
In the laminated film of at least two layers including the polyamide film of the present invention, the polyamide film is preferably disposed in the outermost layer.

The polyamide resin composition of the present invention has good antistatic properties and slipperiness under high humidity by adding a polyether ester amide elastomer, an inorganic filler and a bisamide compound containing a specific electrolyte salt compound. Further, it is possible to produce molded products such as films and stretched films in which characteristics such as transparency and pinhole resistance are balanced in a high dimension.
The polyamide resin composition of the present invention can be used as molded articles such as polyamide films and stretched films.
Although the polyamide film and stretched film obtained from the polyamide resin composition of the present invention have a high utility value alone, it is possible to produce a laminated film having at least two layers in which the polyamide film is disposed in the outermost layer. The film also exhibits the same effect as the single-layer polyamide film. Therefore, due to the problems of generation and accumulation of static electricity and insufficient slip under high humidity, the range of use of the polyamide film that has been limited so far is expanded, and its utility value is extremely large.

The polyamide resin composition of the present invention comprises a polyamide composition (A) 100 parts by weight, an inorganic filler (B) 0.1-1 part by weight, and a bisamide compound (C) 0.03-0.3 part by weight. It is a composition.
The resin composition is based on 100 parts by weight of the polyamide composition (A).
Containing 0.1 to 1 part by weight of the inorganic filler (B), preferably 0.15 to 0.7 part by weight, more preferably 0.2 to 0.5 part by weight,
A resin composition containing the bisamide compound (C) in an amount of 0.03 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight.
If the added amount of the inorganic filler (B) is less than the above value, the effect of improving the slipperiness of the resulting film under high humidity is small, and if it exceeds the above value, the transparency of the molded product such as a polyamide film, Appearance and the like are impaired.
If the addition amount of the bisamide compound (C) is less than the above value, the effect of the present invention cannot be sufficiently obtained, and if it exceeds the above value, the printability of a molded product such as a polyamide film is improved. descend.

The polyamide composition (A) is a composition comprising 70 to 99.5% by weight of a polyamide resin (D) and 30 to 0.5% by weight of a polyamide elastomer composition (E),
Preferably, they are 75 to 98% by weight of the polyamide resin (D) and 25 to 2% by weight of the polyamide elastomer composition (E).
In the polyamide composition (A), if the polyamide elastomer composition (E) is less than the above values, the effect of improving antistatic properties and pinhole resistance is small, whereas if it exceeds the above values, the heat resistance In addition, it is not possible to expect an improvement in the effect commensurate with it, which is not only economically disadvantageous, but also a film having a uniform thickness cannot be formed.

The polyamide resin (D) is polymerized or copolymerized by a known method such as melt polymerization, solution polymerization or solid phase polymerization using a lactam, an aminocarboxylic acid, or a nylon salt composed of a diamine and a dicarboxylic acid as a raw material. Obtainable.
As the polyamide resin (D), a single polymer or copolymer derived from a lactam, an aminocarboxylic acid, or a nylon salt composed of a diamine and a dicarboxylic acid can be used alone or in the form of a mixture.

Examples of the lactam include lactams having 6 or more carbon atoms such as ε-caprolactam, ω-enantolactam, ω-undecane lactam, ω-dodecane lactam, α-pyrrolidone, α-piperidone.
Examples of the aminocarboxylic acid include aminocarboxylic acids having 6 or more carbon atoms such as 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

  Examples of the diamine constituting the nylon salt include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, peptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, Decamethylenediamine, tetradecamethylenediamine, pentadecamethylenediamine, hexadecamethylenediamine, heptacamethylenediamine, octadecamethylenediamine, nonadecamethylenediamine, eicosamethylenediamine, 2 / 3-methyl-1,5-pentane Fats such as diamine, 2-methyl-1,8-octanediamine, 2,2,4 / 2,4,4-trimethylhexamethylenediamine, 5-methyl-1,9-nonanediamine Group diamine, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, 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-trimethyl Fragrances such as cycloaliphatic diamines such as cyclohexanemethylamine (isophoronediamine), bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine, paraxylylenediamine, metaxylylenediamine Group diamine and the like.

  Examples of the dicarboxylic acid constituting the nylon salt include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, Aliphatic dicarboxylic acids such as octadecane dicarboxylic acid, eicosane dicarboxylic acid, 1,3 / 1,4-cyclohexanedicarboxylic acid, dicyclohexylmethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid, isophthal Examples thereof include aromatic dicarboxylic acids such as acid, terephthalic acid, 1,4 / 1,5 / 2,6 / 2,7-naphthalenedicarboxylic acid, and diphenylmethane-4,4′-dicarboxylic acid.

  Specific examples of the polyamide resin (D) include polyamide 6, polyamide 7, polyamide 11, polyamide 12, polyamide 46, polyamide 66, polyamide 69, polyamide 6/10, polyamide 6/11, polyamide 6/12, polyamide 6T, Polyamide 6I, polyamide MXD6, polyamide 6/66 (copolymer of polyamide 6 and polyamide 66, hereinafter the copolymer is also described), polyamide 6/69, polyamide 6/610, polyamide 6/611, polyamide 6/12, polyamide 6 / 612, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 6/66/610, polyamide 6/66/12, polyamide 6/66/612, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6T / 6I, polyamide 66 / 6T 6I and the like. Preferred polyamide resins (D) include polyamide 6, polyamide 12, polyamide 66, polyamide 6/66 in consideration of heat resistance, mechanical strength, transparency, economy, availability, etc. of the obtained molded product. , Polyamide 6/12, and polyamide 6/66/12.

  The relative viscosity of the polyamide resin (D) measured according to JIS K-6920 is preferably 2.0 to 5.0, more preferably 2.5 to 4.5. If the relative viscosity of the polyamide resin (D) is less than the above value, the mechanical properties of the resulting molded product such as a polyamide film may be lowered. On the other hand, when the above value is exceeded, the viscosity at the time of melting increases, and it may be difficult to form a film or the like.

The polyamide resin (D) has no particular restrictions on the type, concentration and molecular weight distribution of its end groups.
One or more of monoamines, diamines, monocarboxylic acids, and dicarboxylic acids can be added in combination as appropriate for molecular weight adjustment and melt stabilization during molding. 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 can be determined appropriately so that the relative viscosity of the finally obtained polyamide falls within the above range.

  The polyamide resin (D) preferably further has a water extraction amount of 1.0% or less measured according to the method for measuring the content of low molecular weight substances specified in JIS K-6920, preferably 0.5% or less. It is more preferable that If the amount of water extraction exceeds the above-mentioned value, adhesion of oligomer components in the vicinity of the T-die is remarkable in film molding and the like, and appearance defects may easily occur due to the generation of die lines and fish eyes due to these deposits. Furthermore, the polyamide resin (D) has a higher hygroscopicity than the olefin resin. When a hygroscopic material is used, an oligomer is generated because the hydrolysis occurs when the raw material is melt-extruded. Since manufacture may become difficult, it is preferable to dry beforehand and to make a moisture content into 0.1 weight% or less.

The polyamide elastomer composition (E) is a composition containing an electrolyte salt compound and a polyamide elastomer (F). The polyamide elastomer composition (E) is composed of 99.99 to 90% by weight of polyamide elastomer (F) and 0.01 to 10% by weight of electrolyte salt compound, and 99.98 to 95% by weight of polyamide elastomer (F) and electrolyte salt. The compound is preferably 0.02 to 5% by weight, more preferably 99.95 to 97% by weight of the polyamide elastomer (F) and 0.05 to 3% by weight of the electrolyte salt compound. When the content of the electrolyte salt compound exceeds the above value, the antistatic performance is inferior. On the other hand, when the content is larger than the above range, the surface appearance of a molded article such as a 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 relative to the number of moles of alkylene oxide in the soft segment (b) of the polyamide elastomer (F). It is desirable that the number of moles of alkali metal or alkaline earth metal cation in the electrolyte salt compound with respect to the alkylene oxide of the soft segment (b) be equal to or lower than the saturated dissolution concentration. When the concentration is higher than the saturated dissolution concentration, it is considered that the electrolyte salt compound component not dissolved in the alkylene oxide of the soft segment (b) does not contribute to the antistatic effect.

The polyamide elastomer (F) is a polyether ester amide elastomer obtained from a polyamide hard segment (a) and a soft segment (b) containing a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5,000. .
The polyamide hard segment (a) of the polyamide elastomer (F) contains 60% by weight or more of the same polyamide-forming unit as that of the polyamide resin (D) in 100% by weight of the polyamide hard segment (a), and contains an aliphatic dicarboxylic acid, a fat The polyamide hard segment (a) contains at least one dicarboxylic acid selected from cyclic dicarboxylic acids and aromatic dicarboxylic acids.
The soft segment (b) of the polyamide elastomer (F) is preferably a polyalkylene oxide represented by the following general formula (2) having a number average molecular weight of 300 to 5,000.

（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.)

（式中、Ｒは炭素数２〜３のアルキレン基、ｎは１〜５０の整数を表す。）

(In the formula, R represents an alkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50.)

  The hard segment (a) of the polyamide elastomer (F) is a polyamide having carboxyl groups at both ends, and is the same polyamide forming unit as the polyamide resin (D). The lactam, aminocarboxylic acid, or diamine and dicarboxylic acid described above are used. The content of the unit composed of the nylon salt composed of an acid is 60% by weight or more, preferably 70% by weight or more, and preferably 80% by weight or more with respect to 100% by weight of the hard segment (a). More preferred. By satisfying the above values, the resulting molded article such as film is excellent in transparency, and when the same polyamide forming unit as the polyamide resin (D) is less than the above value, The transparency is inferior.

  The polyamide-forming unit means a lactam, an aminocarboxylic acid, or a nylon salt composed of a diamine and a dicarboxylic acid forming the polyamide resin (D), and an oligomer obtained therefrom.

The polyamide hard segment (a) of the polyamide elastomer (F) contains 60% by weight or more of the same polyamide forming unit as the polyamide resin (D) in 100% by weight of the polyamide hard segment (a).
The polyamide resin (D) and the polyamide elastomer (F) used in the polyamide composition (A)
It means that the polyamide forming unit of the polyamide hard segment (a) of the polyamide elastomer (F) contains 60% by weight or more of the same polyamide forming unit as the polyamide forming unit of the polyamide resin (D).
For example, when the polyamide resin (D) used in the polyamide composition (A) is polyamide 6, the polyamide forming unit of the polyamide hard segment (a) of the polyamide elastomer (F) is derived from polyamide 6 or equivalent to polyamide 6 A forming unit, for example, ε-caprolactam is 60% by weight or more with respect to 100% by weight of the polyamide hard segment (a).
When the polyamide resin (D) used in the polyamide composition (A) is polyamide 6/12, the polyamide forming unit of the polyamide hard segment (a) of the polyamide elastomer (F) is derived from the polyamide 6 or equivalent to the polyamide 6 The amount of the polyamide-forming unit and the polyamide-forming unit derived from or equivalent to polyamide 12, for example, ε-caprolactam and ω-dodecanactam is 60% by weight based on 100% by weight of the polyamide hard segment (a). % Or more.
Therefore, when the polyamide resin (D) used in the polyamide composition (A) is polyamide 6, the polyamide forming unit of the polyamide hard segment (a) of the polyamide elastomer (F) is derived from the polyamide 12 or a polyamide equivalent to the polyamide 12 When the forming unit is contained in an amount exceeding 40% by weight based on 100% by weight of the polyamide hard segment (a), it is not included in the present invention.

  The dicarboxylic acid of the hard segment (a) of the polyamide elastomer (F) is used as a molecular weight modifier, and in the presence thereof, has the carboxyl groups at both ends by ring-opening polymerization or polycondensation of the polyamide-forming unit by a conventional method. Polyamide is obtained.

  Examples of the dicarboxylic acid of the hard segment (a) of the polyamide elastomer (F) include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, and dodecanedicarboxylic acid. Acid, 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acid such as dicyclohexylmethane-4,4′-dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene Examples include aromatic dicarboxylic acids such as dicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, sodium 3-sulfoisophthalate, and alkali metal salts of 3-sulfoisophthalic acid such as potassium 3-sulfoisophthalate. What was illustrated above may be used independently, or may be used in combination of 2 or more types as appropriate. Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate. Can be mentioned.

  The number average molecular weight of the hard segment (a) of the polyamide elastomer (F) 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 polyamide elastomer (F) itself may be lowered. When the number average molecular weight is more than the above value, the reactivity is lowered. May be required.

Q is an alkylene group having 2 to 4 carbon _{atoms, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) -, - CH 2 CH 2 CH 2 CH 2 - Is mentioned. These can use 1 type (s) or 2 or more types.
In particular, Q is preferable because it has excellent antistatic properties in the case of —CH ₂ CH ₂ —.
R is an alkylene group having 2 to 3 carbon _{atoms, -CH 2 CH 2 -, -} CH 2 CH 2 CH 2 -, - CH 2 CH (CH 3) - and the like. These can use 1 type (s) or 2 or more types.

In the soft segment (b) of the polyamide elastomer (F), the number average molecular weight of the polyalkylene oxide represented by the general formula (1) or the general formula (2) is 300 to 5000, preferably 500 to 4000, It is more preferably 1000 to 3000, and further preferably 1500 to 3000. When the number average molecular weight of the polyalkylene oxide is less than the above value, the antistatic property becomes insufficient. When the number average molecular weight exceeds the above value, the reactivity is lowered, so that a great amount of time is required for producing the polyamide elastomer (F).
As the soft segment (b) of the polyamide elastomer (F), a mixture of n of 1 to 50 represented by the chemical formula (1) or the chemical formula (2) can be used.

  The amount of the soft segment (b) constituting the polyamide elastomer (F) is preferably 20 to 80% by weight based on the total weight of the hard segment (a) and the soft segment (b). More preferably, it is 75% by weight. When the amount of the soft segment (b) is less than the above value, the antistatic property may be inferior. When the amount of the soft segment (b) exceeds the above value, the heat resistance of the polyamide elastomer (F) is lowered. There is a case.

Although the manufacturing method of a polyamide elastomer (F) is not specifically limited, For example, the following manufacturing method [1] or manufacturing method [2] can be illustrated.
Production method [1]: A method in which a polyamide-forming unit and a dicarboxylic acid are reacted to form a hard segment (a), a soft segment (b) is added thereto, and a polymerization reaction is performed at high temperature and under reduced pressure.
Production method [2]: The polyamide-forming unit and dicarboxylic acid forming the hard segment (a) and the soft segment (b) are simultaneously charged into the reaction vessel and subjected to a pressure reaction at high temperature in the presence or absence of water. An intermediate is formed by the following, and then the polymerization reaction of the hard segment (a) and the soft segment (b) is performed under reduced pressure.

  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, zirconyl acetate, and zinc acetate. Examples include organic acid metal salt-based catalysts. It is preferable that the usage-amount of a catalyst is 0.1-5 weight part with respect to the total weight of (a) and (b).

  The relative viscosity (0.5 wt%, m-cresol solution, 25 ° C.) of the polyamide elastomer (F) is preferably 1.2 to 3.0, more preferably 1.3 to 2.5. preferable. When the relative viscosity is less than the above value, the heat resistance may be deteriorated, and it may take a long time to produce the polyamide elastomer (F).

  The electrolyte salt compound contained in the polyamide elastomer composition (E) has almost no humidity dependency and can impart excellent antistatic performance without deteriorating the pinhole resistance of the polyamide film of the present invention. .

The electrolyte salt compound is a metal salt component composed of an alkali metal or alkaline earth metal cation and an ion-dissociable anion.
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 include perhalogenate anions such as perchloric acid and perbromate, halogen acid anions such as chlorate and bromate, halogen anions such as chlorine, bromine, fluorine and iodine, octyl Alkyl sulfonate anions such as sulfonic acid and stearyl sulfonic acid, aryl sulfonic acid anions such as dodecylbenzene sulfonic acid and benzene sulfonic acid, alkyl sulfate anions such as lauryl sulfate and ethyl sulfate, carboxylic acids such as sulfate anion, acetic acid and propionic acid Anions, alkyl phosphate anions, phosphate anions, phosphite anions, nitrate anions, carboxylic acid anions, halide anions such as tetrafluoroboron, hexafluoroarsenic, hexafluorophosphorus, trichloromethanesulfonic acid, trifluoromethanesulfonic acid 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 a perchloric acid anion is more preferable.

Specific examples of the electrolyte salt compound include lithium perchlorate LiClO ₄ , sodium perchlorate NaClO ₄ , lithium trifluoromethanesulfonate Li (CF ₃ SO ₃ ), bis (trifluoromethanesulfonyl) imide lithium Li · N (CF ₃ SO ₂ ) ₂ , sodium bis (trifluoromethanesulfonyl) imide 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 and the like. 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.

In the polyamide elastomer composition (E),
As a method of adding the electrolyte salt compound to the polyamide elastomer (F), in order to effectively disperse it in the composition, it is desirable to disperse it in the polyamide elastomer (F) in advance. Sometimes it is desirable to add and disperse beforehand.
Here, in order to produce the polyamide elastomer (F) in the presence of the electrolyte salt compound, 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, you may add as it is, may melt | dissolve in a polymerization component beforehand, may add, and may also melt | dissolve and add in another solvent.

The polyamide composition (A) is prepared by mixing or kneading the polyamide resin (D) and the polyamide elastomer composition (E) by a known method.
The polyamide composition (A) is produced by further blending various additives as necessary within a range not impairing the characteristics of the present invention, and mixing or kneading by a known method. For example, using a tumbler or a mixer, a dry blend method that is directly added to the polyamide resin raw material at the time of molding, a kneading method in which the polyamide resin raw material is melt kneaded in advance using a uniaxial or biaxial extruder at a concentration used during molding, Or the masterbatch method etc. which knead | mix beforehand with a high concentration at the polyamide resin raw material using a uniaxial or biaxial extruder, dilute this at the time of shaping | molding, etc. are mentioned.

  The inorganic filler (B) is arbitrarily selected from known materials as long as it is a substance that effectively forms fine protrusions on the polyamide film surface during film formation and / or stretching (uniaxial or biaxial). be able to. In addition, the shape and particle diameter of the inorganic filler can be used without particular limitation as long as surface protrusions are formed on the surface and a molded article such as a polyamide film excellent in slipperiness under high humidity can be obtained. . As the shape of the inorganic filler (B), powders, particles, flakes, plates, fibers, needles, cloths, mats, and any other shapes can be used. Is preferred.

The inorganic filler (B) is not limited in the average particle diameter of the inorganic filler (B) as long as the characteristics of the present invention are not impaired, but the average particle diameter is preferably 0.5 to 10 μm.
In addition, when forming a film or the like, the inorganic filler (B) preferably does not substantially contain particles having a particle size exceeding 10 μm, and if a large amount of particles having a particle size exceeding the above value is contained, Eye gel may be generated and the film appearance may be impaired. On the other hand, when a large amount of particles having a particle size smaller than the above value is contained, secondary aggregation tends to occur, and on the contrary, a fish eye gel may be generated. Moreover, even if aggregation can be prevented, it is difficult to obtain the unevenness effect on the film surface, and the slipperiness may not be improved. Therefore, when the particle diameter of the inorganic filler (B) is not suitable for the present invention, it is desirable to perform pulverization and classification in advance. In particular, when paying attention to slipperiness under high humidity, the average particle diameter is more preferably 1 to 5 μm.

As the inorganic filler (B), silica such as gel type silica, precipitated type silica, spherical silica, talc, kaolin, montmorillonite, zeolite, mica, glass flake, wollastonite, potassium titanate, magnesium sulfate, sepiolite, zonolite , Aluminum borate, glass beads, calcium silicate, calcium carbonate, titanium oxide, barium sulfate, zinc oxide, magnesium hydroxide and the like.
Among these, talc, kaolin, and silica are preferable from the viewpoint of easy dispersibility, and the film from which the silica is obtained is excellent in transparency and slipperiness, and more preferable.
One type of inorganic filler (B) may be used, or two or more types may be used in combination. The combined use of two or more inorganic fillers is a preferred embodiment for securing slipperiness, particularly slipperiness under high humidity, while ensuring transparency, and is a recommended method for blending inorganic fillers. . For example, the case where silica and kaolin, silica and talc are used in combination is exemplified. When used in combination, it is less than the amount blended alone to improve slippage under high humidity, without causing problems such as a decrease in transparency of the molded product such as film and the occurrence of fish eyes, and under high humidity. It is possible to improve the slip in

Silica used as the inorganic filler (B) contains silicon dioxide represented by SiO ₂ · nH ₂ O as a main component. The method is roughly classified into two types, that is, wet method silica and dry method silica, and any of them can be used in the present invention. The primary particles are of so-called submicron order, which is called soft silica in which these primary particles are aggregated to form secondary particles or tertiary particles, and hard silica whose primary particle size is already 1 μm or more. However, when the film is stretched, soft silica is more preferable.

The specific surface area of silica used is a value measured by the BET method ^is preferably 50m ² / g~1000m 2 / ^g, more preferably ^{75m 2 / g~800m 2 / g,} 100m 2 / More preferably, it is g-700m < ² > / g.
When the specific surface area is less than the above value, the amount of surface functional groups is small, the interaction with the polyamide resin is small, and only silica is detached when forming a molded product such as a film, so-called powder blowing state In some cases, this may cause roll stains in the film production apparatus, etc., or may cause ink bleeding during printing or contamination of the package contents. On the other hand, when the specific surface area exceeds the above value, the amount of surface functional groups is excessively increased, causing excessive interaction with the polyamide resin, which may cause gels and fish eyes. Although the use of silica has been described above, the same aspect can be followed for the use of other inorganic fillers.

The added amount of the inorganic filler (B) is such that the finally obtained molded product such as a polyamide film has excellent slipperiness under high humidity as described later, and has transparency and surface glossiness. Any range within which optical characteristics can be obtained is acceptable.
The amount of the inorganic filler (B) to be added varies depending on the type, shape, average particle diameter, and the like of the inorganic filler to be used, or stretching conditions (stretching ratio, stretching method, etc.) after film formation, and cannot be generally described. However, the addition amount is preferably 0.1 to 1 part by weight, more preferably 0.15 to 0.7 part by weight, based on 100 parts by weight of the polyamide composition (A). More preferably, it is in the range of 2 to 0.5 parts by weight. If the added amount of the inorganic filler (B) is less than the above value, the effect of improving the slipperiness of the resulting film under high humidity is small, and if it exceeds the above value, the transparency and appearance of the polyamide film are impaired. It is.

  The inorganic filler (B) needs to have good dispersibility with the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E) when mixed with the polyamide composition (A). . If the dispersibility is poor, the inorganic filler agglomerates, resulting in poor appearance such as reduced transparency and frequent fish eyes in the molded product such as polyamide film, etc. This is not preferable because there is a risk of lowering the function of the product and, further, reducing productivity in melt molding.

  The inorganic filler (B) is for improving the dispersibility with the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E), or for suppressing the dirt on the die during film melt molding. If necessary, it is preferable to use an inorganic filler surface-treated with a surface treatment agent.

The type and amount of the surface treatment agent for the inorganic filler (B) can be appropriately selected and used depending on the type of the inorganic filler (B) to be used. For example, in the case of silica, an amino group or An alkoxysilane compound containing an epoxy group, mercapto group, isocyanato group, hydroxyl group or the like can be preferably used.
Specific examples of the surface treatment agent for the inorganic filler (B) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-β- (aminoethyl). -Γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminodithiopropyltrihydroxysilane, γ- (polyethyleneamino) propyltrimethoxysilane, N-β- Amino group-containing alkoxysilane compounds such as (aminopropyl) -γ-aminopropylmethyldimethoxysilane, N- (trimethoxysilylpropyl) -ethylenediamine, γ-dibutylaminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ -Ureidopropyltrime Toxicisilane, ureido group-containing alkoxysilane compounds such as γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3, 4-epoxycyclohexyl) epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and γ-isocyanatopropyltriethoxysilane Γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-i Examples include isocyanato group-containing alkoxysilane compounds such as cyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane, and hydroxyl-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. . These can use 1 type (s) or 2 or more types. Among these, amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane are preferable.

  For example, in the case of silica, the addition amount of the surface treatment agent of the inorganic filler (B) is preferably 1 to 30 parts by weight with respect to 100 parts by weight of silica (dry matter basis), and 2 to 10 parts by weight. More preferably, it is 3 to 8 parts by weight. If the addition amount of the surface treatment agent is less than the above value, the affinity between the silica and the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E) becomes insufficient, and the dispersibility May get worse. On the other hand, if the addition amount exceeds the above-mentioned value, the effect of improving the dispersibility of the added silica with the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E) is hardly increased, but finally In some cases, the mechanical properties of the polyamide film obtained may be impaired, or the surface treating agent may bleed out from a molded product such as a film.

  The surface treatment method of the inorganic filler (B) is not particularly limited, but a method of adding a predetermined amount of the surface treatment agent diluted with an appropriate amount of water under heating and stirring, and a surface treatment agent of a predetermined amount, respectively. A known method such as a method of mixing silica and the above-mentioned silica with a suitable apparatus such as a Henschel mixer and then heat-treating at a predetermined temperature can be applied.

  As a method of adding the inorganic filler (B) to the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E), the polymerization step of the polyamide resin (D) or the polyamide elastomer composition (E) is used. Addition method during polymerization, polyamide composition (A), polyamide resin (D) or polyamide elastomer composition (E) is kneaded in advance at a high concentration using a single or twin screw extruder and molded The so-called masterbatch method, which is sometimes diluted and used, the kneading and mixing method in which the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E) is kneaded in advance at the additive concentration used for molding, molding A drive that is sometimes added to a polyamide composition (A), a polyamide resin (D), or a polyamide elastomer composition (E). Command method are possible, it may be adopted another addition method.

  Mixing of the polyamide composition (A), the polyamide resin (D) or the polyamide elastomer composition (E) and the inorganic filler (B) is performed in the form of pellets, powdered polyamide composition (A), polyamide resin (D) or A method of blending the polyamide elastomer composition (E) and the inorganic filler at room temperature using a high-speed rotary mixer such as a Henschel mixer or a low-speed rotary mixer such as a cone blender or a tumbler, or the blended material further with a Banbury mixer , Super mixer, mixing roll, twin-screw continuous mixer, Brabender plastograph, kneader, single-screw extruder, twin-screw extruder, etc., at a temperature at which melting of the blend proceeds sufficiently and does not decompose It is carried out by a method known per se, such as a melt kneading method.

The bisamide compound (C) is a compound represented by the following general formula (3) and / or general formula (4), wherein R ¹ is a divalent hydrocarbon residue, R ² and R ³ are A monovalent hydrocarbon residue, R ⁴ and R ⁵ represent a hydrogen atom or a monovalent hydrocarbon residue.

  The bisamide compound (C) represented by the general formula (3) is obtained by a reaction between a diamine and a monocarboxylic acid, and representative examples thereof include alkylene bis fatty acid amide and arylene bis fatty acid amide. The raw material diamines include ethylene diamine, propylene diamine, tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine and other alkylene diamines, phenylene diamine And arylene diamines such as naphthalene diamine and arylene alkyl diamines such as xylylene diamine. These can use 1 type (s) or 2 or more types. Examples of the raw material monocarboxylic acid include stearic acid, hexanoic acid, octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, alkydic acid, behenic acid, oleic acid, elaidic acid, and montanic acid. These can use 1 type (s) or 2 or more types. Examples of the bisamide compound (C) represented by the general formula (3) include N, N′-methylenebisstearic acid amide, N, N′-ethylene bisstearic acid amide, and N, N′-ethylene bisbehenic acid amide. preferable.

The bisamide compound (C) represented by the general formula (4) is obtained by a reaction between a monoamine and a dicarboxylic acid, and representative examples include dioctadecyl dibasic acid amide. The raw material monoamines include ethyleneamine, methylamine, butylamine, hexylamine, decylamine, pentadecylamine, octadecylamine, alkylamines such as dodecylamine, arylamines such as aniline and naphthylamine, aralkylamines such as benzylamine, and cyclohexylamine. And the like, and the like. These can use 1 type (s) or 2 or more types. Examples of the raw material dicarboxylic acid include terephthalic acid, p-phenylenedipropionic acid, succinic acid, adipic acid and the like. These can use 1 type (s) or 2 or more types.
As the bisamide compound (C) represented by the general formula (4), N, N′-dioctadecyladipic acid amide is preferable.
The bisamide compound (C) can use 1 type (s) or 2 or more types. .

  As a blending method of the bisamide compound (C), it is prepared by blending in a polyamide composition (A), a polyamide resin (D) or a polyamide elastomer composition (E) as necessary, and mixing or kneading by a known method. Is done. For example, using a tumbler or a mixer, a dry blend method in which a polyamide composition (A), a polyamide resin (D) or a polyamide elastomer composition (E) is directly added, a polyamide composition (A), a polyamide resin (D) or A kneading method in which the polyamide elastomer composition (E) is added and melt-kneaded using an extruder or kneader, or the polyamide composition (A), polyamide resin (D) or polyamide elastomer composition (E) at a high concentration in advance. And a masterbatch method in which the product is diluted during molding and used.

  The polyamide resin composition, polyamide composition (A), polyamide resin (D) or polyamide elastomer composition (E) of the present invention is used in the present invention within a range that does not impair the properties of the molded product such as a film obtained. Heat stabilizer except antioxidant (B) and bisamide compound (C) to be used, antioxidant, UV absorber, weathering agent, lubricant, filler, nucleating agent, plasticizer, foaming agent, antiblocking agent, anticlouding agent , Flame retardants, dyes, pigments, stabilizers, coupling agents and the like.

The molded product such as the polyamide film of the present invention may contain a nonionic, cationic or amphoteric surfactant for the purpose of further improving the antistatic effect.
Nonionic surfactants include higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycol type nonionic surfactants such as polypropylene glycol ethylene oxide adducts, polyethylene oxide, Examples include fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbit and sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol type nonionic surfactants such as aliphatic amides of alkanolamines.
Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts.
Examples of the amphoteric surfactant include aminocarboxylic acid type amphoteric surfactants such as higher alkylaminopropionate, and betaine type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. These can use 1 type (s) or 2 or more types.

The polyamide resin composition of the present invention can contain an olefin copolymer, a modified product thereof, and an elastomer within a range that does not impair the transparency of a molded product such as a film.
In particular, in the case of obtaining a polyamide film from the polyamide resin composition of the present invention, for the purpose of further improving pinhole resistance, an olefin copolymer, a modified product thereof, Elastomers can be included.
Examples of the olefin copolymer include ethylene / α-olefin copolymer having 3 to 10 carbon atoms, ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl acetate. Examples thereof include a partially saponified product of a copolymer, an ethylene / α, β-unsaturated carboxylic acid copolymer, and an ionomer polymer. These can use 1 type (s) or 2 or more types.
Elastomers include those other than those specified in the present invention, such as polyether ester amide elastomers, polyester amide elastomers, polyether amide elastomers, and other polyamide-based elastomers. Polystyrene phases at both ends, hydrogenated polyolefins as rubber intermediate phases, and polystyrene phases. Styrenic elastomer which is a block copolymer carrying a cross-linking point. These can use 1 type (s) or 2 or more types.

Since the polyamide resin composition of the present invention is excellent in melt moldability and excellent moldability, it is possible to produce molded articles such as films.
The polyamide resin composition of the present invention can obtain molded products having various shapes such as a film shape, a filament shape, a plate shape, a sheet shape, and a rod shape by a molding method such as injection molding, extrusion molding, and blow molding.
The polyamide resin composition of the present invention has low humidity dependency, imparts antistatic properties that last for a long time, is excellent in slipperiness under high humidity, and is excellent in transparency. In particular, the polyamide resin composition of the present invention is preferably used after being formed into a film and a sheet because of excellent pinhole resistance.
The polyamide resin composition of the present invention is coated with a part or all of the outer surface of the molded product or disposed on a part or all of the outer surface, is imparted with antistatic properties and is excellent in slipperiness under high humidity. It is preferable because a molded product can be obtained.
The molded product obtained from the polyamide resin composition of the present invention can be used for food materials, electrical parts, electronic parts, electrical equipment, electronic equipment, etc., and storage materials and packaging materials for transporting and storing them. it can.

The polyamide resin composition of the present invention can be formed by applying a known film production method. For example, a casting method in which the polyamide resin composition of the present invention is melt kneaded with an extruder, extruded into a flat film shape with a T-die or a coat hanger die, cast on a casting roll surface, and cooled to produce a film, ring-shaped A tubular method for producing a film by air-cooling or water-cooling a tubular material melt-extruded into a cylinder by a die can be used, and an unstretched film can be obtained.
Furthermore, an unstretched film is uniaxial or biaxial, and a stretched polyamide film can be obtained by stretching simultaneously or sequentially. For example, a film produced by the casting method is a tenter simultaneous biaxial stretching method in which an unstretched sheet is stretched simultaneously in the longitudinal and transverse directions with a tenter-type simultaneous biaxial stretching machine, and an unstretched sheet melt-extruded from a T-die is stretched in a roll-type stretching machine. An example is a sequential biaxial stretching method in which the film is stretched in the direction and then stretched in the transverse direction with a tenter type stretching machine. There is a tubular stretching method in which a tubular sheet formed from an annular die is stretched simultaneously in the longitudinal and lateral directions by gas pressure. The stretching step may be carried out continuously following the production of the polyamide film, or the polyamide film may be wound once and then stretched as a separate step.

  The polyamide film produced from the polyamide resin composition of the present invention can be used after being stretched. Stretching conditions such as the stretching ratio and stretching temperature of the film vary depending on the intended use. Usually, in the case of uniaxial stretching, the stretching ratio is preferably 1.5 to 5.0 times, and preferably 1.8 to 3.5. More preferably, it is double. In the case of the tenter-type biaxial stretching method and the tubular method, the stretching ratio is preferably 1.5 to 4.0 times in the longitudinal direction and 1.5 to 4.0 times in the transverse direction. It is more preferable that the direction is 2.5 to 4.0 times. The stretching temperature is preferably 30 to 210 ° C, and more preferably 50 to 200 ° C.

The film stretched by the above method can be given dimensional stability at room temperature by subsequent heat treatment. The heat treatment temperature in this case is preferably selected in a range with 110 ° C. as the lower limit and 5 ° C. lower than the melting point of the polyamide resin (D) as the upper limit. A stretched film having the above can be obtained. The polyamide film of the present invention preferably has poor heat shrinkage or substantially does not have it. Therefore, in the heat treatment conditions performed after stretching, the heat setting temperature is preferably 150 ° C. or higher, more preferably 180 to 220 ° C., and the relaxation rate is preferably within 20% in the width direction. More preferably, it is 3 to 10%.
The stretched film that has been sufficiently heat-set by the heat treatment operation is cooled and wound up according to a conventional method.

  Further, the polyamide film and the stretched film 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, and heat sealing.

  The polyamide film produced from the polyamide resin composition of the present invention and this stretched film are excellent in antistatic properties, slipperiness under high humidity, transparency, and pinhole resistance, and can be used alone. Furthermore, it is possible to add more film characteristics by laminating with other thermoplastic resin films. Specifically, a polyamide film and a stretched film can be used as a laminated film by laminating a thermoplastic resin layer on at least one side of the stretched film. It is preferable from the viewpoint of prevention and slipperiness.

  The polyamide film produced from the polyamide resin composition of the present invention and the laminated film containing one layer of this stretched film are produced by laminating another substrate on one or both sides of the polyamide film of the present invention and this stretched film. be able to. The laminated film is laminated by, for example, the polyamide film of the present invention and a method of melt-extruding a thermoplastic resin to the stretched film, or a method of melt-extruding the resin composition of the polyamide film of the present invention to a film or sheet of thermoplastic resin or the like. , A method of co-extrusion of a resin composition of a polyamide film of the present invention and another thermoplastic resin, a polyamide film of the present invention and a stretched film and a film of another thermoplastic resin, etc., an organic titanium compound, an isocyanate compound, Examples of the method include dry lamination using a known adhesive such as a polyester compound and a polyurethane compound.

  As the polyamide film produced from the polyamide resin composition of the present invention and the thermoplastic resin laminated with the stretched film, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), Propylene homopolymer, α-olefin copolymer having 2 to 10 carbon atoms excluding propylene / propylene, ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (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 coalesced (EEA) and acrylic acids thereof Methacrylic acid, 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 Carboxyl groups such as heptene-2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2,2,1] Contains functional groups such as epoxy groups such as acid anhydride groups such as -5-heptene-2,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. In addition, the above-mentioned polyolefin resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PE ), Polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystalline polyester (LCP) and other polyester resins, 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) Resins, polyketone resins such as polyetheretherketone (PEEK), polyallyletherketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), polynitrile resins such as methacrylonitrile / styrene / butadiene copolymer (MBS), polymethyl methacrylate (PMMA) , Polymethacrylate resins such as polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer , Polyvinyl chloride resins such as vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer Coalescence ( ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / Vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer (PFA) and other fluororesins, polycarbonate (PC) and other polycarbonate resins, thermoplastic Examples include polyimide resins such as polyimide (PI), polyamideimide (PAI), and polyetherimide, thermoplastic polyurethane resins, polyester elastomers, and polyurethane elastomers. It is also possible to laminate the polyamide resin (D) defined in the present invention. From the viewpoint of film strength and gas barrier properties, polymetaxylylene adipamide (polyamide MXD6) or ethylene / vinyl acetate copolymer saponification It is preferable to laminate a product (EVOH).

  The polyamide film produced from the polyamide resin composition of the present invention, this stretched film, or a laminated film including a layer of this film, in addition to the thermoplastic resin layer, paper, metal, metal foil, woven fabric, non-woven fabric, metal Cotton, wood, etc. can be laminated.

  The thickness of the polyamide film produced from the polyamide resin composition of the present invention and the stretched film is not particularly limited as long as it is appropriately selected depending on the application. However, if the thickness of the polyamide film is large, the strength of the polyamide film is improved. However, since transparency and pinhole resistance are lowered, the thickness of the polyamide film is preferably 5 to 100 μm, more preferably 10 to 80 μm, and more preferably 10 to 60 μm in consideration of these. More preferably. In the case of a laminated film, the thickness of the polyamide film layer is preferably 2 to 100 μm, more preferably 5 to 80 μm, and further preferably 5 to 60 μm.

  The polyamide film produced from the polyamide resin composition of the present invention, the stretched film, and the laminated film thereof can be used for food packaging, packaging of electronic / electrical parts, electrical / electronic equipment, etc., storage, etc. .

  In the following, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples without departing from the gist of the present invention. The polyamide resin, polyether ester amide elastomer, inorganic filler, bisamide compound, evaluation film preparation method, and various evaluation methods used in the examples are shown.

[Polyamide resin used]
(D) Polyamide resin (D-1) Polyamide 6 (UBE NYLON 1022B, relative viscosity 3.35 manufactured by Ube Industries, Ltd.)
(D-2) Polyamide 6/66 (UBE NYLON 5034B, relative viscosity 4.05 manufactured by Ube Industries, Ltd.)
(D-3) Polyamide 12 (UBESTA 3030XA, Ube Industries, Ltd., relative viscosity 2.24)

[Polyamide elastomer composition used]
(E-1) Polyetheresteramide elastomer composition (manufactured by Ciba Specialty Chemicals Co., Ltd., a polyetheresteramide elastomer obtained from irgastat P22, ε-caprolactam, adipic acid and polyethylene oxide, containing sodium perchlorate, Sodium chlorate content is 2.8% by weight)
(E-2) polyether ester amide elastomer composition (manufactured by Ciba Specialty Chemicals Co., Ltd., irgastat P18, polyether ester amide elastomer obtained from ω-dodecane lactam, adipic acid and polyethylene oxide, containing sodium perchlorate, (The sodium perchlorate content is 2.8% by weight)

[Polyamide elastomer used]
(E-3) Polyether ester amide elastomer (polyester ester amide elastomer obtained from Daicel Degussa Co., Ltd. Vestamido E40-S3, ω-dodecane lactam, dodecanedicarboxylic acid and polytetramethylene oxide)

[Inorganic filler used]
(B-1) Manufacture of silica master chip Silica surface-treated with 20 kg of ε-caprolactam, 2 kg of water, and 1000 g of γ-aminopropyltriethoxysilane in a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer (Japan) Silica Co., Ltd. product, Nipsil E220A, average particle diameter of about 2 μm) was added and maintained at 100 ° C., and stirred at this temperature until the reaction system became uniform. Subsequently, the mixture was heated to 260 ° C. with stirring, maintained at a pressure of 1.5 MPa for 1 hour, further released to normal pressure over 1 hour, and further polymerized for 1 hour. When the polymerization was completed, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain polyamide resin pellets in which the gel type silica was uniformly dispersed. Subsequently, this pellet was immersed in hot water at 95 ° C. to remove unreacted monomers, and then dried under reduced pressure to obtain a silica master chip having a relative viscosity of 2.57 (hereinafter, this silica master chip was referred to as (B-1) Called).

(B-2) Manufacture of silica master chip (B-1) In the manufacture of silica master chip, the same method as (B-1) manufacture of silica master chip except that ε-caprolactam was changed to ω-dodecanactam Thus, a silica master chip having a relative viscosity of 1.70 was obtained (hereinafter, this silica master chip is referred to as (B-2)).

(B-3) Production of kaolin master chip (B-1) Silica surface-treated with γ-aminopropyltriethoxysilane (manufactured by Nippon Silica Co., Ltd., Nipsil E220A, average particle size of about 2 μm) ) Was changed to kaolin (manufactured by Mizusawa Chemical Co., Ltd., Shilton AMT25, average particle size of about 2.5 μm) in the same manner as in the production of (B-1) silica master chip, with a relative viscosity of 2.54. The kaolin master chip was obtained (hereinafter, this kaolin master chip is referred to as (B-3)).

[Bisamide compounds used]
(C-1) Manufacture of bisamide master chip Polyamide 6 (Ube Industries, UBE NYLON 1011FB, relative viscosity: 2.20) and ethylenebisstearic acid amide (Nippon Kasei Co., Ltd., SLIPAX E) After 3% dry blending, this was supplied to a biaxial melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt kneaded at a cylinder temperature of 200 to 250 ° C., and the molten resin was extruded into a strand shape Thereafter, this was introduced into a water tank, cooled, cut and vacuum dried to obtain a bisamide master chip (hereinafter, this bisamide master chip is referred to as (C-1)).

(C-2) Manufacture of bisamide master chip (C-1) In manufacture of bisamide master chip, polyamide 6 (manufactured by Ube Industries, UBE NYLON 1011FB, relative viscosity 2.20) was replaced with polyamide 12 (Ube Industries, Ltd.) (C-1) A bisamide master chip was obtained in the same manner as in the production of the bisamide master chip except that the viscosity was changed to UBESTA 3014B (relative viscosity 1.67). C-2)).

(C-3) Manufacture of bisamide master chip (C-1) In the manufacture of bisamide master chip, ethylenebisstearic acid amide (Nihon Kasei Co., Ltd., Sripax E) was replaced with ethylene bisbehenic acid amide (Nippon Kasei Co., Ltd.). A bisamide master chip was obtained in the same manner as in the production of (C-1) bisamide master chip except that the product was changed to Slipax B) (hereinafter, this bisamide master chip is referred to as (C-3)).

[Antistatic property]
1) Surface Specific Resistance After conditioning the evaluation film at 23 ° C. and 50% relative humidity for 3 days, using an insulation resistance meter (Yokogawa Hewlett-Packard Co., Ltd., Model 4329A), 23 ° C. and relative humidity 50 The surface resistivity was measured under the conditions of applied voltage 500V and 30 seconds in a% atmosphere. When the surface resistivity was 10 ¹⁴ or less, it was judged that the antistatic property was excellent.

2) Electrostatic half-life After the conditioning film was conditioned at 23 ° C. and 60% relative humidity for 3 days, it was measured at 23 ° C. and 50% relative humidity using a static Honestometer (manufactured by Sisid Electric Co., Ltd., H-0110). % Atmosphere was measured under the conditions of an applied voltage of 10 kV and a distance between samples of 20 mm. When the charged half-life was 10 seconds or less, it was judged that the antistatic property was excellent.

[transparency]
The haze, which is a measure of transparency, was measured according to ASTM D-1003 using a direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP). When the haze value was 8.0% or less, it was judged that the transparency was excellent.

[Pinhole resistance (repeated bending fatigue test)]
The number of pinholes generated in the film after an evaluation film was subjected to a bending test 1000 times at 0 ° C. according to MIL-E-131C using a gelbo flex tester with a thermostat (manufactured by Rigaku Corporation). Was measured using a pinhole detector (manufactured by Sanko Electronics Co., Ltd.). When the number of pinholes was 10 or less, it was judged that the pinhole resistance was excellent.

[Slipperiness (coefficient of dynamic friction)]
According to ASTM D-1894, the dynamic coefficient of friction of the film / particulate material film is measured at 23 ° C., 50% RH, 23 ° C., and 80% RH, respectively. However, in order to determine the change of the dynamic friction coefficient depending on the measurement atmosphere (humidity), the polyamide film sample portion was placed in a constant temperature and humidity chamber. The measurement was performed 5 times, and the average value was obtained. Moreover, when the dynamic friction coefficient in the humidity 80% RH atmosphere was 0.35 or less, it was judged that it was excellent in the slipperiness in high humidity.

Example 1
Polyamide resin (D-1) and polyetheresteramide elastomer (E-1) are supplied to a twin-screw extruder (manufactured by Nippon Steel Works, TEX30 type) at the ratio shown in Table 1, and the extruder is set. The mixture was melt kneaded, granulated, and dried under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm. A composition prepared by adding silica master chip (B-1) and bisamide master chip (C-1) to 100 parts by weight of the pellets and blending the inorganic filler and the bisamide compound in the proportions shown in Table 1 is used. In a 40 mmφ extruder equipped with a circular die, it is melted at an extrusion temperature of 260 ° C. and taken up while being cooled with water at 20 ° C. A polyamide unstretched film 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 biaxially stretched polyamide film having a thickness of 15 μm. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Examples 2-3)
In Example 1, biaxial stretching was carried out in the same manner as in Example 1 except that the blending ratio of the polyamide resin (D-1) and the polyether ester amide elastomer (E-1) was changed to the ratio shown in Table 1. A polyamide film was obtained. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

Example 4
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the polyamide resin (D-1) was changed to the polyamide resin (D-2) in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Example 5)
In Example 1, the polyamide resin (D-1) is changed to the polyamide resin (D-3), the polyetheresteramide elastomer (E-1) is changed to (E-2), and the silica master chip (B-1) is changed to ( A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the bisamide master chip (C-1) was changed to (C-2) and the extrusion temperature was changed to 240 ° C. in B-2). The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Examples 6 to 7)
In Example 1, the compounding ratio of the silica master chip (B-1) was changed, and the addition amount of the inorganic filler was changed to the ratio shown in Table 1, and the biaxially stretched polyamide film was prepared in the same manner as in Example 1. Got. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Examples 8 to 9)
A biaxially stretched polyamide film was prepared in the same manner as in Example 1, except that the blending ratio of the bisamide master chip (C-1) was changed and the addition amount of the bisamide compound was changed to the ratio shown in Table 1. Got. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Example 10)
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the silica master chip (B-1) was changed to the kaolin master chip (B-3) in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Example 11)
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the bisamide master chip (C-1) was changed to (C-3) in Example 1. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Example 12)
In Example 1, the same method as in Example 1 except that the silica master chip (B-1) and the kaolin master chip (B-3) were used in combination, and the addition amount of the inorganic filler was changed to the ratio shown in Table 1. A biaxially stretched polyamide film was obtained. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Example 13)
In Example 1, bisamide master chips (C-1) and (C-3) were used in combination, and the addition amount of the bisamide compound was changed to the ratio shown in Table 1, and the same procedure as in Example 1 was repeated. An axially stretched polyamide film was obtained. The physical property measurement results of the obtained biaxially stretched polyamide film are shown in Table 1.

(Comparative Example 1)
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the polyetheresteramide elastomer (E-1) was not blended. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Examples 2-3)
In Example 1, biaxial stretching was carried out in the same manner as in Example 1 except that the blending ratio of the polyamide resin (D-1) and the polyether ester amide elastomer (E-1) was changed to the ratio shown in Table 1. A polyamide film was obtained. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Example 4)
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the polyether ester amide elastomer (E-1) was changed to (E-3) in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Example 5)
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the polyetheresteramide elastomer (E-1) was changed to (E-2) in Example 1. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Example 6)
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the silica master chip (B-1) was not used. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Example 7)
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the bisamide master chip (C-1) was not used. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Examples 8-9)
A biaxially stretched polyamide film was prepared in the same manner as in Example 1, except that the blending ratio of the silica master chip (B-1) was changed and the amount of inorganic filler added was changed to the ratio shown in Table 2. Got. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Comparative Example 10)
A biaxially stretched polyamide film was prepared in the same manner as in Example 1, except that the blending ratio of the bisamide master chip (C-1) was changed and the addition amount of the bisamide compound was changed to the ratio shown in Table 2. Got. Table 2 shows the physical property measurement results of the obtained biaxially stretched polyamide film.

(Example 14)
Polyamide resin (D-1) and polyether ester amide elastomer (E-1) are supplied to a twin screw extruder (manufactured by Nippon Steel Works, TEX30 type) at the ratio shown in Table 3, and the extruder is set. The mixture was melt kneaded, granulated, and dried under the conditions of a temperature of 250 ° C. and a screw rotation speed of 100 rpm. Raw material polyamide resin composition in which silica master chip (B-1) and bisamide master chip (C-1) are added to 100 parts by weight of the pellets, and the inorganic filler and bisamide compound are blended in the proportions shown in Table 3. And using a polyamide resin (D-1), in a 40 mmφ extruder equipped with a circular three-layer die, melted at an extrusion temperature of 260 ° C., and cooled with water at 20 ° C. A tubular laminated polyamide unstretched film which was substantially amorphous and not oriented 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 are released from the clip, the ears are trimmed and wound up, and the composition of (outer layer) / (intermediate layer) / (inner layer) is raw material polyamide resin composition / polyamide resin (D-1) / raw material polyamide resin A three-layer laminated biaxially stretched polyamide film of the composition (layer thickness 4 μm / 7 μm / 4 μm) was obtained. Table 3 shows the physical property measurement results of the obtained laminated biaxially stretched polyamide film.

Claims (9)

100 parts by weight of the polyamide composition (A),
A polyamide resin composition containing 0.1 to 1 part by weight of an inorganic filler (B) and 0.03 to 0.3 part by weight of a bisamide compound (C),
(I) Polyamide composition (A) contains 70-99.5 wt% of polyamide resin (D) and 30-0.5 wt% of polyamide elastomer composition (E),
(II) The polyamide elastomer composition (E) contains 99.99 to 90% by weight of the polyamide elastomer (F) and 0.01 to 10% by weight of the electrolyte salt compound,
(III) The polyamide elastomer (F) is a polyether ester amide obtained from a polyamide hard segment (a) and a soft segment (b) containing a polyalkylene oxide represented by the following general formula (1) having a number average molecular weight of 300 to 5000 An elastomer,
(IV) The polyamide hard segment (a) of the polyamide elastomer (F) contains 60% by weight or more of the same polyamide forming unit as that of the polyamide resin (D) with respect to 100% by weight of the polyamide hard segment (a), and is aliphatic. A polyamide resin composition comprising a polyamide hard segment (a) containing at least one dicarboxylic acid selected from dicarboxylic acids, alicyclic dicarboxylic acids and aromatic dicarboxylic acids.

(In the formula, Q represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 50.)   A homopolymer or copolymer of polyamide resin (D) comprising at least one polyamide-forming unit selected from the group consisting of ε-caprolactam, ω-dodecanlactam, 12-aminododecanoic acid, hexamethylenediamine adipate The polyamide resin composition according to claim 1, which is a coalescence. Polyamide elastomer (F)
[1] Polyamide hard segment (a) containing 60% by weight or more of the same polyamide forming unit as that of the polyamide resin (D) with respect to 100% by weight, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid and 3-sulfoisophthalic acid A polyamide hard segment (a) containing at least one dicarboxylic acid selected from the group consisting of sodium,
And [2] a polyetheresteramide elastomer obtained from a soft segment (b) containing a polyalkylene oxide represented by the following general formula (2) having a number average molecular weight of 300 to 5,000: Item 3. The polyamide resin composition according to Item 2.

(In the formula, R represents an alkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50.)   The polyamide resin composition according to any one of claims 1 to 3, wherein the inorganic filler (B) contains at least one selected from the group consisting of silica, kaolin and talc.   The bisamide compound (C) contains at least one selected from the group consisting of ethylene bis stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide and ethylene bis erucic acid amide. The polyamide resin composition according to any one of the above.   A molded product obtained from the polyamide resin composition according to claim 1.   The molded product according to claim 6, wherein the molded product is a film.   The molded article according to claim 6, wherein the molded article is a stretched film. A laminated film comprising at least two layers of a molded product layer of the film according to claim 7 and claim 8 and a thermoplastic resin layer.