JP2012041527A - Polyamide resin composition and film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide film enhancing slipperiness under high humidity, without deteriorating adhesiveness and wettability to other material, when layered or laminated with other materials, and a polyamide resin composition of a raw material for the film.SOLUTION: This polyamide resin composition contains a polyamide resin (A), an inorganic filler (B), and a bis-amide compound (C), the (A) comprises 60-98 pts.mass of component (a) and 40-2 pts.mass of component b, the component (a) is a polyamide resin having 8.0 mass% or more of saturated water absorption under water at 23°C, the component b is a polyamide resin having 3,000 MPa or more of flexural modulus measured based on ASTM D-790 at 23°C in 50% of relative humidity (RH), the (B) is an inorganic filler particle surface-treated with an organosiloxane, the (C) is a reaction product of a 14C or more C fatty acid with a diamine, and contents thereof are 0.01-0.4 pt.mass of the (B), and 0.02-25 pts.mass of the (C), per 100 pts.mass of the (A), in the polyamide resin composition.

Description

  The present invention relates to a polyamide film and a raw material polyamide resin composition.

Polyamide film is excellent in gas barrier properties, toughness, mechanical properties, and thermal properties, so it can be used for packaging films, especially in the food packaging field. It is used in various fields as a constituent material for laminated films produced by coextrusion. In such a polyamide film, the slip property is one of the important required properties from the viewpoint of film productivity, quality and commercial value.
If the slipperiness is poor, not only will the trouble occur during the post-processing steps such as the laminating step and the printing step, but the film supply will not proceed smoothly even in the final packaging step, resulting in packaging failure.
In particular, in the packaging of foods containing a lot of moisture, slipperiness under high humidity is regarded as important because it is used in a high humidity environment.

However, the polyamide film tends to deteriorate in slipperiness in a high humidity environment, and various methods have been proposed as means for improving the slipperiness of the polyamide film in high humidity.
For example, Patent Document 1 discloses a method of using silica having a specific pore volume in a polyamide resin,
Patent Document 2 includes a method of adding inorganic particles such as a combination of silica and talc,
Patent Document 3 includes a method of adding crosslinked organic polymer fine particles,
In Patent Document 4, a combined use method of layered silicate and inorganic particles,
Patent Document 5 includes a method of using a specific size silica and a specific fatty acid bisamide,
Patent Document 6 discloses a method in which the number of protrusions on the film surface is set to a specific range, and the surface is hydrophobized by adding an organic lubricant,
Patent Document 7 discloses a method in which the number of protrusions on the film surface is in a specific range, and the area ratio of microvoids contained in the surface layer is not more than a specific value,
Patent Document 8 includes a method of using polyglycerol fatty acid ester or polyglycerol condensed hydroxy fatty acid ester and inorganic particles,
Patent Documents 9 and 10 include a method of using a specific fatty acid bisamide and a polyglycerol fatty acid ester,
Patent Document 11 discloses a method in which a melt-extruded polyamide resin is directly water-cooled and solidified within a specific temperature range,
In Patent Documents 12 and 13, a method of laminating a slippery layer on a polyamide film is proposed as a method (means) for improving the slipperiness of the polyamide film under high humidity.

JP-A-9-143283 JP 7-138471 A Japanese Patent Laid-Open No. 9-241504 JP 2004-149555 A JP 2002-348465 A JP-A-10-168310 Japanese Patent Laid-Open No. 9-272748 JP 2000-63578 A JP 2003-155359 A JP 2004-137394 A JP 2001-64415 A Japanese Patent No. 3624492 JP-A-9-156046

Many methods for improving the slipperiness of polyamide films under high humidity have been proposed, but increasing the amount of organic lubricants such as higher fatty acid bisamide compounds to obtain sufficient slipperiness increases the organicity on the film surface. The bleed out of the lubricant becomes prominent, and when the film is laminated or laminated with another material, the adhesion and wettability with the other material is deteriorated, which adversely affects processing such as printing, vapor deposition, and lamination.
In addition, the method of improving the slipperiness by laminating the slippery layer on the polyamide film requires a surface treatment step and a coating step of the slippery layer, which requires a capital investment accompanying the manufacturing process. Incurs increased costs.

The subject of the present invention is
When laminating and laminating with other materials, the slipperiness under high humidity has been improved without deteriorating the adhesion and wettability with other materials. It is also said that they are made compatible.) To provide a polyamide film and a polyamide resin composition as a raw material thereof.

The present invention includes the following contents.
(1) A polyamide resin composition comprising a polyamide resin (component A), an inorganic filler (component B), and a bisamide compound (component C),
Component A consists of 60 to 98 parts by mass of component a and 40 to 2 parts by mass of component b,
The component a is a polyamide resin having a saturated water absorption rate of 23% by weight in water of 8.0% by mass or more,
The component b is a polyamide resin having a flexural modulus of 3,000 MPa or more measured in accordance with ASTM D-790 at 23 ° C. and a relative humidity (RH) of 50%.
Component B is obtained by subjecting inorganic filler particles to surface treatment with organosiloxane,
The component C is obtained by reacting a diamine with a fatty acid having 14 or more carbon atoms,
The content of the components A, B and C is
For 100 parts by mass of component A,
Component B is 0.01 to 0.4 parts by mass,
The polyamide resin composition whose said component C is 0.02-25 mass parts.
(2) A polyamide film comprising the polyamide resin composition according to (1).
(3) At least
A layer (x) comprising the polyamide film according to (2),
A layer (y) comprising the component a,
The layer (x) and the layer (y) are in contact;
A polyamide laminated film in which the layer (x) is disposed in the outermost layer.

According to the present invention,
When laminating or laminating with other materials, a polyamide film having improved slipperiness under high humidity without deteriorating adhesion and wettability with other materials and a polyamide resin composition as a raw material thereof. Can be provided.

The polyamide resin composition of the present invention is
Flexural elasticity measured in accordance with ASTM D-790 at 60 ° C to 98 parts by mass of a polyamide resin (a) having a saturated water absorption rate of 8.0% by mass or more at 23 ° C and 23 ° C and 50% relative humidity (RH). Surface treatment is performed with 100 parts by mass of polyamide resin (A) composed of 40-2 parts by mass of polyamide resin (b) having a rate of 3,000 MPa or more and 0.01-0.4 parts by mass of organopolysiloxane. Inorganic polyamide (B) and a polyamide resin composition comprising 0.02 to 0.25 parts by mass of a bisamide compound (C) composed of a fatty acid having 14 or more carbon atoms, ,
A polyamide resin composition comprising a polyamide resin (component A), an inorganic filler (component B), and a bisamide compound (component C),
Component A consists of 60 to 98 parts by mass of component a and 40 to 2 parts by mass of component b,
The component a is a polyamide resin having a saturated water absorption rate of 23% by weight in water of 8.0% by mass or more,
The component b is a polyamide resin having a flexural modulus of 3,000 MPa or more measured in accordance with ASTM D-790 at 23 ° C. and a relative humidity (RH) of 50%.
Component B is obtained by subjecting inorganic filler particles to surface treatment with organosiloxane,
The component C is obtained by reacting a diamine with a fatty acid having 14 or more carbon atoms,
The content of the components A, B and C is
For 100 parts by mass of component A,
Component B is 0.01 to 0.4 parts by mass,
The component C is 0.02 to 25 parts by mass.

  The polyamide film using the polyamide resin composition of the present invention is suitable for a soft packaging material, excellent in transparency and printability, particularly excellent in slipperiness under high humidity and excellent in continuous productivity.

[Component a]
Component a is a polymer having an amide bond (—CONH—) in the main chain,
The saturated water absorption at 23 ° C. in water is 8.0% by mass or more.
The saturated water absorption rate of component a is measured by the following method.
A test piece (resin piece) having a length of 80 mm, a width of 80 mm, and a thickness of 1 mm is molded, and the pre-test mass (mass before water absorption) is measured in the moisture content state (dry as molded) of the test piece immediately after molding. Thereafter, it is immersed in water at 23 ° C. for 1,000 hours.
Thereafter, the sample is taken out from the water, the surface adhering moisture is wiped off, and the sample is left in a constant temperature and constant humidity (23 ° C., relative humidity (RH) 50%) atmosphere for 30 minutes, and then the mass after test (mass after water absorption) is measured.
The increment of the mass after water absorption relative to the mass before water absorption was taken as the water absorption amount, and the ratio of the water absorption amount relative to the mass before water absorption was measured as the saturated water absorption rate (% by mass).

From the viewpoint of the thermal and mechanical properties of the resulting polyamide film, in component a, the content of units derived from caprolactam is preferably 50 mol% or more based on the total polymerization units of component a. More preferably, it is 70 mol% or more, More preferably, it is 75 mol% or more, More preferably, it is 100 mol%.
Component a is specifically a polycaproamide (polyamide 6) or a copolymer containing 50 mol% or more of units derived from caprolactam from the viewpoint of the thermal and mechanical properties of the resulting polyamide film. It is also possible to copolymerize other polymerized units excluding those derived from caprolactam.

  Examples of other polymerized units include lactams other than caprolactam, aminocarboxylic acids, or units derived from nylon salts composed of diamines and dicarboxylic acids.

The lactam excluding caprolactam is preferably a lactam having 4 to 12 carbon atoms, and examples thereof include enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like.
The aminocarboxylic acid is preferably an aminocarboxylic acid having 6 to 12 carbon atoms, and examples thereof include 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.
These can use 1 type (s) or 2 or more types.

In the nylon salt consisting of diamine and dicarboxylic acid, the diamine may be an aliphatic diamine having 2 to 20 carbon atoms, an alicyclic diamine having 6 to 20 carbon atoms, or an aromatic diamine having 6 to 12 carbon atoms. Can be mentioned.
Examples of the aliphatic diamine having 2 to 20 carbon atoms include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1 , 14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2- / 3-methyl-1,5-pentanediamine, 2 -Methyl-1,8-octanediamine, 2,2,4- / 2,4,4-trimethyl-1,6-hexanedi Min, 5-methyl-1,9-nonanediamine or the like.
Examples of the alicyclic diamine having 6 to 20 carbon atoms include 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-cyclo Pentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-bis (3-aminopropyl) piperazine, 1,4-bis (2-aminoethyl) piperazine, norbornane Examples include dimethylamine and tricyclodecane dimethylamine.
Examples of the aromatic diamine having 6 to 12 carbon atoms include m- / p-xylylenediamine.
These diamines can be used alone or in combination of two or more.

In the nylon salt comprising diamine and dicarboxylic acid, the dicarboxylic acid may be an aliphatic dicarboxylic acid having 2 to 24 carbon atoms, an alicyclic dicarboxylic acid having 8 to 24 carbon atoms, or an aromatic having 8 to 20 carbon atoms. Group dicarboxylic acids.
Examples of the aliphatic dicarboxylic acid having 2 to 24 carbon atoms include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, and pentadecanedioic acid. , Hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid and the like.
Examples of the alicyclic dicarboxylic acid having 8 to 24 carbon atoms include 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, and 2,5- / 2,6. -Norbornane dicarboxylic acid etc. are mentioned.
Examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms include isophthalic acid, terephthalic acid, 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid, and the like.
These dicarboxylic acids can be used alone or in combination of two or more.

Specific examples of component a include polyamide 6, polyamide 6/66, polyamide 6/69, polyamide 6/610, polyamide 6/612, polyamide 6/12, polyamide 6/66/12, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 6 / IPD6, polyamide 6 / IPDT, polyamide 6 / MXD6, polyamide 6 / MXDT. Among these, polyamide 6, polyamide 6/66, polyamide 6/12, polyamide 6 / IPD6, polyamide 6 from the viewpoint of heat resistance, mechanical strength, transparency, economy, and availability of the obtained polyamide film. / IPDT and polyamide 6/66/12 are preferable, and polyamide 6, polyamide 6/66, polyamide 6/12, and polyamide 6/66/12 are more preferable.
In addition, the said name of the specific example of the component a is based on JISK6920-1: 2000 "Plastic-polyamide (PA) molding and extrusion material-Part 1: The system of a designation system and the basis of specification description."

There are no particular restrictions on the type, concentration and molecular weight distribution of the end group of component a, and as molecular weight regulators, monocarboxylic acids such as acetic acid and stearic acid, meta One or two or more of diamines such as range amine and isophorone diamine, monoamine, and dicarboxylic acid can be added as appropriate.
For example, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine,
Cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine,
Aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine,
Aliphatic diamines such as 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine,
Cycloaliphatic diamines such as 1,3- / 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, isophoronediamine,
aromatic diamines such as m- / p-phenylenediamine, m- / p-xylylenediamine, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, Aliphatic monocarboxylic acids such as stearic acid, pivalic acid, isobutyric acid,
Alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid,
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, α- / β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid,
Aliphatic dicarboxylic acids such as adipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid,
Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid,
Examples thereof include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid.
These can use 1 type (s) or 2 or more types.
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 polyamide resin to be finally obtained falls within the following range.

Component a is manufactured using a batch reactor, a single- or multi-tank continuous reactor, a tubular continuous reactor, a single-screw kneading extruder, a kneading reaction extruder such as a twin-screw kneading extruder, etc. It can be manufactured with a device.
Examples of the polymerization method include melt polymerization, solution polymerization, and solid phase polymerization.
In these polymerization methods, polymerization can be carried out by repeating normal pressure, reduced pressure, and pressure operation, and they can be used alone or in appropriate combination.

  The relative viscosity of component a measured in accordance with JIS K-6920 under the conditions of a polymer concentration of 1% by mass and a temperature of 25 ° C. in 96% by mass sulfuric acid should ensure the mechanical properties of the resulting polyamide film. From the viewpoint of ensuring the moldability by setting the viscosity at the time of melting to an appropriate range, it is preferably 2.0 to 5.0, more preferably 2.5 to 4.5.

[Component b]
Component b is a polymer having an amide bond (—CONH—) in the main chain,
At 23 ° C and relative humidity (RH) 50%,
The flexural modulus measured according to ASTM D-790 is 3,000 MPa or more, more preferably the flexural modulus is 3,100 MPa or more, more preferably 3,200 MPa or more. 3,000 MPa or less, more preferably 7,000 MPa or less, even more preferably 6,000 MPa or less, even more preferably 3,000 to 8,000 MPa, and 3,100 to 7 It is more preferable that it is 1,000,000 MPa, and it is further more preferable that it is 3,200-6,000 MPa.

  Component b is a polymer comprising a unit derived from m-xylylenediamine and / or p-xylylenediamine and a unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms (component b-1 ) And / or a polymer (component b-2) comprising units derived from terephthalic acid and / or isophthalic acid and units derived from an aliphatic diamine having 6 to 12 carbon atoms.

  In the component b-1, as the aliphatic dicarboxylic acid having 6 to 12 carbon atoms, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 2-methyladipic acid 2,2-dimethylglutaric acid, 2,2,4 / 2,4,4-trimethyladipic acid, and 2-butylsuberic acid. These 1 type (s) or 2 or more types can be used. Among these, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid are preferable, and adipic acid is more preferable from the viewpoint of mechanical strength and availability of the obtained polyamide film.

  Component b-1 contains other units except for units derived from m-xylylenediamine and / or p-xylylenediamine and units derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms. It is also possible to polymerize.

As other diamine units other than units derived from xylylenediamine selected from m-xylylenediamine and p-xylylenediamine,
1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1 , 9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1, 16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2- / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4 -/ 2,4,4-trimethyl-1,6-hexanediamine, aliphatic such as 5-methyl-1,9-nonanediamine Amine,
1,3- / 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, 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 (isophoronediamine), bis ( Alicyclic diamines such as aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, tricyclodecane dimethylamine,
m- / p-phenylenediamine, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedimethylamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4 ' -Diphenylmethanediamine, 3,3'-diethyl-4,4'-diphenylmethanediamine, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, etc. Examples thereof include units derived from aromatic diamines. These can use 1 type (s) or 2 or more types.

Examples of other dicarboxylic acid units other than units derived from aliphatic dicarboxylic acids having 6 to 12 carbon atoms include aliphatics such as malonic acid, succinic acid, glutaric acid, tridecanedioic acid, octadecanedioic acid, and eicosanedioic acid. Dicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid,
Examples thereof include units derived from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types.

Other units include units derived from lactams such as caprolactam and dodecane lactam,
Examples thereof include units derived from aminocarboxylic acids such as aliphatic aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid.
These can use 1 type (s) or 2 or more types.

Specific examples of component b-1 include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene pimeramide (polyamide MXD7), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide). MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene azelamide (polyamide PXD9), polyparaxili Homopolymers such as Lensebacamide (polyamide PXD10), polyparaxylylene decanamide (polyamide PXD12), metaxylylene / paraxylylene adipamide copolymer (polyamide MXD6 / PXD6), metaxylylene Paraxylylene pimeramide copolymer (polyamide MXD7 / PXD7), metaxylylene / paraxylylenes beramide copolymer (polyamide MXD8 / PXD8), metaxylylene / paraxylylene azelamide copolymer (polyamide MXD9 / PXD9), Examples include copolymers such as a metaxylylene / paraxylylene sebacamide copolymer (polyamide MXD10 / PXD10), a metaxylylene / paraxylylene decanediamide copolymer (polyamide MXD12 / PXD12), and polymetaxylylene adipamide ( Polyamide MXD6) is preferred.
In addition, the name in the parenthesis of the specific example of the above b-1 is JIS K6920-1: 2000 “Plastic—Polyamide (PA) molding and extrusion material—Part 1: Basis of designation system and specification notation” based on.

  In component b-2, examples of the aliphatic diamine having 6 to 12 carbon atoms include 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1, 10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2- / 3-methyl-1,5-pentanediamine, 2,2,4- / 2,4,4-trimethyl-1, 6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2- / 2,3- / 2,4- / 2,5-dimethyl-heptanediamine, 2- / 3- / 4- Methyl-1,8-octanediamine, 1,3- / 1,4- / 2,2- / 2,4- / 3,3- / 3,4- / 4,4- / 4,5-dimethyl- 1,8-octanediamine, 5-methyl-1,9-nonane Amine, 2/3-butyl-1,8, and the like. These can use 1 type (s) or 2 or more types. Among these, from the viewpoint of mechanical strength and availability of the obtained polyamide film, 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, and 1,12-dodecanediamine are preferable. 1,6-hexanediamine is more preferred.

  Component b-2 can be copolymerized with other units other than units derived from terephthalic acid and / or isophthalic acid and units derived from aliphatic diamines having 6 to 12 carbon atoms. .

As other dicarboxylic acid units other than units derived from terephthalic acid and / or isophthalic acid,
Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2,4- / 2,4,4-trimethyladipic acid, Pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanediic acid Aliphatic dicarboxylic acids such as acids, octadecanedioic acid, eicosanedioic acid,
Alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, dicyclohexanemethane-4,4′-dicarboxylic acid, norbornane dicarboxylic acid,
1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid, 1,3- / 1,4-phenylenedioxydiacetic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid Acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′- Examples thereof include units derived from aromatic dicarboxylic acids such as biphenyl dicarboxylic acid and 4,4′-triphenyl dicarboxylic acid.
These can use 1 type (s) or 2 or more types.

Examples of diamine units other than units derived from aliphatic diamines having 6 to 12 carbon atoms include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,13-triamine. Aliphatic diamines such as decane diamine, 1,14-tetradecane diamine, 1,15-pentadecane diamine, 1,16-hexadecane diamine, 1,17-heptadecane diamine, 1,18-octadecane 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-trimethylcyclohexane Cycloaliphatic diamines such as methylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, tricyclodecane dimethylamine,
m- / p-phenylenediamine, m- / p-xylylenediamine, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedimethylamine, 4,4'-diaminodiphenylmethane, 2, Examples thereof include units derived from aromatic diamines such as 2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl ether.
These can use 1 type (s) or 2 or more types.

Other units include units derived from lactams such as caprolactam and dodecane lactam,
Examples thereof include units derived from aminocarboxylic acids such as aliphatic aminocarboxylic acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid, and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid.
These can use 1 type (s) or 2 or more types.

Specific examples of component b-2 include polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 6I / 6, polyamide 6T / 6, polyamide 6I / 6, polyamide 6T / 66, polyamide 6I / 66, polyamide Examples thereof include 6T / 12, polyamide 6I / 12, polyamide 6T / 6I / 12, and polyamide 6T / 6I is preferable.
In addition, the said name of the specific example of component b-2 is based on JISK6920-1: 2000 "Plastic-Polyamide (PA) molding and extrusion material-Part 1: Basis of designation system and specification notation". .

Component b is a polyamide production apparatus such as a batch type reaction kettle, a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, a kneading reaction extruder such as a biaxial kneading extruder, and the like. Can be manufactured.
Examples of the polymerization method include melt polymerization, solution polymerization, and solid phase polymerization.
In these polymerization methods, polymerization can be carried out by repeating normal pressure, reduced pressure, and pressure operation, and they can be used alone or in appropriate combination.

  The relative viscosity of component b measured according to JIS K-6920 under the conditions of a polymer concentration of 1% by mass and a temperature of 25 ° C. in 96% by mass sulfuric acid should ensure the mechanical properties of the resulting polyamide film. From the viewpoint of ensuring the moldability by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.8 to 3.5, and more preferably 1.9 to 3.0.

[Component A]
Component A is suitable for flexible packaging with the viewpoint of achieving both wettability and slipperiness of the polyamide resin composition, further improving the slipperiness under high humidity, and the elastic modulus of the obtained polyamide film within an appropriate range. From the viewpoint of obtaining a polyamide film having good bending fatigue resistance,
It consists of component a and component b, and the mixing ratio of both is based on 100 parts by mass of component A,
The amount of component a is 60 to 98 parts by mass, preferably 65 to 96 parts by mass, more preferably 75 to 95 parts by mass, and still more preferably 79 to 94 parts by mass,
The compounding quantity of the component b is 40-2 mass parts, 35-4 mass parts is preferable, 25-5 mass parts is more preferable, 21-6 mass parts is further more preferable.
That is, the component A is used for flexible packaging with the viewpoint of achieving both wettability and slipperiness of the polyamide resin composition, further improving the slipperiness under high humidity, and the elasticity of the resulting polyamide film within an appropriate range. From the viewpoint of obtaining a polyamide film that is suitable and has good bending fatigue resistance,
It consists of component a and component b, and the mixing ratio of both is 60 to 98 parts by mass, preferably 65 to 96 parts by mass, and 75 to 95 parts by mass with respect to 100 parts by mass of component A. More preferably, 79-94 mass parts is more preferable, content of the component b is 40-2 mass parts, 35-4 mass parts is preferable, 25-5 mass parts is more preferable, 21-6 mass parts is further preferable.

[Component B]
Component B in the present invention is an inorganic filler whose inorganic filler particles are surface-treated with organosiloxane, and the shape of the inorganic filler particles constituting Component B is not particularly limited, and is spherical, ellipsoidal, flaky, It may be in the form of a plate, fiber, needle, cloth, mat, collar, or any other shape, but is preferably spherical, ellipsoidal, or plate-like, and is suitable for polyamide film From the viewpoint of imparting, it is preferable that the protrusion is formed on the surface.

The average particle size of the inorganic filler particles is not particularly limited, but in order to ensure the transparency of the polyamide film and not impair the appearance of the polyamide film while ensuring the effect of improving the slipperiness of the resulting polyamide film, The thickness is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, further preferably 1 to 10 μm, and further preferably 2 to 5 μm.
The average particle diameter of the inorganic filler particles refers to the volume average particle diameter measured by the Coulter counter method. When the average particle diameter does not conform to the above range, it is desirable to perform pulverization or classification in advance. Moreover, as long as an average particle diameter satisfy | fills the said value, it is also possible to use together the inorganic filler particle from which a particle size differs.

The specific surface area of the inorganic filler particles, from the viewpoint of ensuring the expression effect of the surface treatment with organopolysiloxane (surface treatment agent) is preferably from 5~1,000m ² / g, is 10~800m ² / g It is more preferable that it is 15-500 m < ² > / g, and it is still more preferable that it is 18-400 m < ² > / g. Here, the specific surface area means a value measured by the BET method.

  Inorganic filler particles include silica, talc, kaolin, montmorillonite, zeolite, mica, glass flake, wollastonite, sepiolite, zonolite, glass beads, calcium silicate, potassium titanate, magnesium sulfate, aluminum borate, calcium carbonate, Examples thereof include titanium oxide, barium sulfate, zinc oxide, and magnesium hydroxide. These can use 1 type (s) or 2 or more types. Among these, talc, kaolin, zeolite, and silica are preferable from the viewpoint of easy dispersibility.

The inorganic filler particles are more preferably silica from the viewpoint of transparency and slipperiness of the obtained polyamide film.
Silica is mainly composed of silicon dioxide represented by SiO ₂ , and is roughly classified according to its production method into two types, wet method silica and dry method silica, and any of them can be used.
Dry silica is generally made by flame hydrolysis. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane may be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state.
On the other hand, wet method silica is further classified into precipitation method silica, gel method silica, and sol method silica according to the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through filtration, water washing, drying, pulverization and classification. The secondary particles of silica produced by this method become loose agglomerated particles, and particles that are relatively easy to grind are obtained.
Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During the ripening, the fine particles dissolve and reprecipitate so as to bind other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure.
The sol method silica is also called colloidal silica, and is obtained by heating and aging a silica sol obtained through metathesis of sodium silicate acid or the like through an ion exchange resin layer.

  The organopolysiloxane used as the surface treatment agent for inorganic filler particles is represented by the following formula (1):

In formula (1), R ^{1 to} R ⁴ each independently represent a hydrogen atom or an organic group, m and n are natural numbers of 1 or more, and the total number of m and n (m + n) is 5 to 500. It is preferably 10 to 300, more preferably 20 to 200. The ratio of m and n (n / m) is determined by the type and content of the organic group to be introduced in consideration of the affinity between the polyamide resin to be used and the inorganic filler particles, and is 1/100 to 10 Preferably, it is 1 / 50-5.

Although it does not specifically limit as said organic group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 2-ethylbutyl group, octyl group etc. Alkyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group of diphenyl group, aralkyl group such as benzyl group, phenylethyl group, phenylpropyl group, cycloalkyl group such as cyclohexyl group, cyclopentyl group, etc. Hydrocarbon groups in which some or all of the hydrogen atoms are substituted with halogen atoms, substituted or unsubstituted hydroxyl groups, siloxy groups, alkoxy groups, alkoxycarbonyl groups, carboxyl groups, mercapto groups, epoxy groups, (meth) acryloxy group, an amino _{group, -O -, - (CH 2} O) p -, - (OCH _{) P -, - (CH 2} O) p CH 2 - structural units containing an ether binding site, such _{as, -CO -, - COCO -,} - CO (CH 2) p CO -, - CO (C 6 H 4) Examples thereof include a structural unit containing a carbonyl group such as CO-, a structural unit containing an amide bond site, a structural unit containing an ester bond site, and a substituent containing a structural unit containing a ketone bond site. p represents an integer of 1 to 30.
Among these, R ^{1 to} R ⁴ are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group from the viewpoints of stability during production or use, and safety and health. 10 to 10 alkyl groups, aryl groups, and aralkyl groups are more preferable, alkyl groups having 1 to 6 carbon atoms or aryl groups are more preferable, and methyl groups are further preferable.

Examples of the organopolysiloxane include dimethyl polysiloxane, methyl hydrogen polysiloxane, methylphenyl polysiloxane, and various modified polysiloxanes.
Various modified polysiloxanes include silanol-modified polysiloxanes with silanol groups introduced at both ends of the polysiloxane skeleton, fluorine-modified polysiloxanes with fluoroalkyl groups introduced into the side chains of the polysiloxane skeleton, and side chains of the polysiloxane skeleton. Alkyl-modified polysiloxanes with long-chain alkyl groups introduced into them, aralkyl-modified polysiloxanes with aralkyl groups introduced into the side chains of the polysiloxane skeleton, and fatty acid ester modifications with higher fatty acid ester groups introduced into the side chains of the polysiloxane skeleton Polysiloxane, a fatty acid amide-modified polysiloxane having a higher fatty acid amide group introduced into the side chain of the polysiloxane skeleton, a polyether having a polyether group such as polyethylene oxide or polypropylene oxide introduced at both ends or side chains of the polysiloxane skeleton Strange Both polysiloxane, amino-modified polysiloxane with amino groups introduced at both ends or side chains of the polysiloxane skeleton, epoxy-modified polysiloxane with epoxy groups introduced at both ends or side chains of the polysiloxane skeleton, and both polysiloxane skeletons Epoxy-polyether-modified polysiloxane having an epoxy group and a polyether group introduced at the terminal or side chain, phenol-modified polysiloxane having a phenolic hydroxyl group introduced at both ends of the polysiloxane skeleton, or both ends or sides of the polysiloxane skeleton Carboxyl-modified polysiloxane with a carboxyl group introduced into the chain, (meth) acrylate-modified polysiloxane with a (meth) acryl group introduced at both ends of the polysiloxane skeleton, and an alkoxy group introduced at both ends of the polysiloxane skeleton Alkoxy modified poly Siloxane, carbinol-modified polysiloxane carbinol group introduced into both terminals or side chains of the polysiloxane backbone, mercapto-modified polysiloxane which mercapto group is introduced at both ends or side chains of the polysiloxane skeleton. These can use 1 type (s) or 2 or more types.
Among these, dimethylpolysiloxane, methylhydrogenpolysiloxane, and methylphenylpolysiloxane are preferable, and dimethylpolysiloxane is more preferable from the viewpoint of availability and safety and health.

  Furthermore, the kinematic viscosity at 25 ° C. of the organopolysiloxane is preferably 5 to 1,000 cSt from the viewpoint of easy processability and uniform treatment of the surface of the inorganic filler particles to prevent generation of coarse aggregated particles. More preferably, it is 8 to 600 cSt.

  The treatment amount of the organopolysiloxane ensures the effect of improving slipperiness under high humidity, good affinity with the polyamide resin, dispersibility, and from the viewpoint of preventing bleeding out of the organopolysiloxane to the polyamide film, It is preferably 0.5 to 15 parts by mass, more preferably 1 to 12 parts by mass, and further preferably 2 to 11 parts by mass with respect to 100 parts by mass of the inorganic filler particles (dry matter basis). preferable.

  The method of treating the inorganic filler particles with the organopolysiloxane is not particularly limited, but the inorganic filler particles and the organopolysiloxane are added to a solvent such as water or alcohol and mixed uniformly using a high shear mixer such as a super mixer. After that, when the wet treatment method in which the surface treatment is performed by removing the solvent, or when the inorganic filler particles are pulverized by a fluid energy pulverizer such as a micronizer or a jet mill, the organopolysiloxane is added so as to be uniform. And a dry processing method in which drying is performed at a predetermined temperature after stirring. Usually, compressed air, heated compressed air, steam or the like is used as the fluid.

[Component C]
Component C is represented by the following general formula (2)

(Wherein R ⁵ is a hydrocarbon group, R ⁶ and R ⁷ are hydrocarbon groups having 14 or more carbon atoms, and R ⁸ and R ⁹ are hydrogen atoms or hydrocarbon groups). It is obtained by a reaction between a diamine and an aliphatic monocarboxylic acid (fatty acid) having 14 or more carbon atoms, and representative examples thereof include alkylene bis fatty acid amides and arylene bis fatty acid amides. Examples of the raw material diamine include alkylene diamine, arylene diamine, and arylene alkyl diamine.

Examples of the alkylene diamine include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine and the like.
Examples of the arylene diamine include m- / p-phenylenediamine, 1,4- / 1,5- / 2,6- / 2,7-naphthalenediamine, and the like.
Examples of the arylene alkyl diamine include m- / p-xylylenediamine.
These diamines can be used alone or in combination of two or more.

  Examples of the aliphatic monocarboxylic acid having 14 or more carbon atoms as raw materials include myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, behenic acid, erucic acid, serotic acid, and montan. An acid, a mellic acid, etc. are mentioned. These can use 1 type (s) or 2 or more types.

  Component C is preferably an alkylene bis-fatty acid amide from the viewpoint of the slipperiness and transparency of the resulting polyamide film. Among these, N, N′-methylene bis-stearic amide, N, N′-ethylene bis-stearic amide N, N'-ethylenebisbehenamide is preferred.

From the viewpoint of achieving both wettability and slipperiness of the polyamide film obtained by the polyamide resin composition, the polyamide resin composition of the present invention comprises components A, B and C,
For 100 parts by mass of component A,
From the viewpoint of ensuring the effect of improving the slipperiness of the polyamide film obtained by the polyamide resin composition, and the amount of the component B added is 0.01 to 0. 4 parts by mass, preferably 0.04 to 0.35 parts by mass, more preferably 0.06 to 0.28 parts by mass, and 0.09 to 0.25 parts by mass. More preferably,
From the viewpoint of ensuring the effect of improving the slipperiness of the polyamide film obtained by the polyamide resin composition, the blending amount of the component C is 0.02 to 25 parts by mass from the viewpoint of not impairing the printability and adhesiveness of the obtained polyamide film. Yes, it is preferably 0.05 to 0.20 parts by mass, more preferably 0.07 to 0.18 parts by mass, and even more preferably 0.08 to 0.16 parts by mass.
Moreover, from the viewpoint of achieving both wettability and slipperiness of the polyamide film obtained by the polyamide resin composition, the total amount of components A, B and C in the thermoplastic resin compounded in the polyamide resin composition is 80 to It is preferably 100% by mass, more preferably 85 to 99.8% by mass, and further preferably 90 to 99.5% by mass.
That is, from the viewpoint of achieving both wettability and slipperiness of the polyamide film obtained by the polyamide resin composition, the polyamide resin composition includes components A, B and C,
For 100 parts by mass of component A,
From the viewpoint of ensuring the effect of improving the slipperiness of the polyamide film obtained by the polyamide resin composition and preventing the generation of eye grease during film formation, the content of the component B is 0.01 to 0.00. 4 parts by mass, preferably 0.04 to 0.35 parts by mass, more preferably 0.06 to 0.28 parts by mass, and 0.09 to 0.25 parts by mass. More preferably,
From the viewpoint of ensuring the effect of improving the slipperiness of the polyamide film obtained by the polyamide resin composition, the content of the component C is 0.02 to 25 parts by mass from the viewpoint of not impairing the printability and adhesiveness of the obtained polyamide film. Yes, it is preferably 0.05 to 0.20 parts by mass, more preferably 0.07 to 0.18 parts by mass, and even more preferably 0.08 to 0.16 parts by mass.
Moreover, from the viewpoint of achieving both wettability and slipperiness of the polyamide film obtained by the polyamide resin composition, the total content of components A, B and C in the thermoplastic resin in the polyamide resin composition is 80 to 100% by mass. It is preferable that it is 85-99.8 mass%, and it is still more preferable that it is 90-99.5 mass%.

[Production of polyamide resin composition]
Hereinafter, suitable production conditions for the polyamide resin composition will be described.
In the production of component A, the method of blending and mixing component a and component b is not particularly limited, and various conventionally known methods can be employed.
For example, it can be produced by a method of dry blending the two, a method of melt kneading them together with other components blended as necessary.
The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

There is no restriction | limiting in particular as a method of adding the component B or the component C to the component a or the component b, The various methods conventionally known are employable. For example, a polymerization internal addition method that is added at an arbitrary stage of the polymerization process of component a or component b, or a high-concentration component B or component C is previously added to component a or component b using a uniaxial or biaxial extruder. So-called masterbatch method that uses kneading and diluting at the time of molding,
A kneading method in which component B and component C are kneaded into component A at the additive concentration during molding,
A dry blend method in which predetermined amounts of Component B and Component C are added to Component a or Component b at the time of molding can be used.
The blending of component B and component C into component a or component b may be performed simultaneously or separately.

  In the polyamide resin composition of the present invention obtained by the above method, various additives and modifiers that are usually blended within a range that does not impair the properties of the obtained polyamide film, for example, a heat stabilizer, ultraviolet absorption Agent, light stabilizer, antistatic agent, lubricant, anti-blocking agent, filler, tackifier, sealing property improver, antifogging agent, crystal nucleating agent, mold release agent, plasticizer, crosslinking agent, foaming agent, coloring Agents (pigments, dyes, etc.) can be added, and for the purpose of improving the bending fatigue resistance, olefin copolymers, modified products thereof, elastomers, and the like can also be added.

  It is preferable to add a hydroxy fatty acid magnesium salt to the polyamide resin composition in order to prevent occurrence of eyelids. Hydroxy fatty acid magnesium salt is a salt of hydroxy saturated or unsaturated fatty acid carboxylic acid and magnesium, specifically, hydroxy lauric acid magnesium salt, hydroxy myristic acid magnesium salt, hydroxy palmitic acid magnesium salt, hydroxy stearic acid magnesium salt, Examples thereof include magnesium hydroxybehenate. These can use 1 type (s) or 2 or more types.

  The blending amount of the hydroxy fatty acid magnesium salt is 0.003 to 0.3 with respect to 100 parts by mass of the (A) polyamide resin from the viewpoint of ensuring the effect of preventing eye grease without impairing the transparency and printability of the polyamide film. It is preferable that it is a mass part, It is more preferable that it is 0.004-0.2 mass part, It is further more preferable that it is 0.005-0.1 mass part.

  Furthermore, the polyamide resin composition has an improved bending fatigue resistance such as an olefin copolymer, a modified product thereof, and an elastomer for the purpose of improving the bending fatigue resistance within a range that does not impair the transparency of the polyamide film. Materials can be included. As the olefin copolymer, ethylene / α-olefin copolymer having 3 to 10 carbon atoms, ethylene / α, β-unsaturated carboxylic acid ester copolymer, ethylene / vinyl acetate copolymer, ethylene / acetic acid Examples thereof include a partially saponified vinyl copolymer, an ethylene / α, β-unsaturated carboxylic acid copolymer, and an ionomer polymer. Examples of modified olefin copolymers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Carboxyl groups such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, Citraconic anhydride, acid anhydride groups such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, Examples of the polyolefin-based copolymer include functional groups such as epoxy groups such as glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

  The elastomers include polyamide elastomers such as polyester elastomers, polyether ester amide elastomers, polyether amide elastomers, block copolymers in which both ends have a polystyrene phase, hydrogenated polyolefin as the rubber intermediate phase, and the polystyrene phase serves as a crosslinking point. Examples thereof include styrene elastomers that are polymers. These can use 1 type (s) or 2 or more types.

  In order to ensure the effect of improving the bending fatigue resistance and not impair the transparency of the resulting polyamide film, the blending amount of the olefin copolymer and its modified product or elastomer is (A) 100 parts by mass of the polyamide resin. On the other hand, it is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 2 to 7 parts by mass.

[Polyamide film]
There is no restriction | limiting in particular as a method of manufacturing a polyamide film using the polyamide resin composition of said this invention (henceforth it may describe as a raw material polyamide resin composition), A well-known film manufacturing method is used. Can be applied.
For example, a raw material polyamide resin composition 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. Examples include a tubular method in which a tubular product melt-extruded into a cylindrical shape is air-cooled or water-cooled to produce a film, and the like.
The obtained polyamide film can be used as an unstretched film, but is preferably a biaxially stretched film from the viewpoint of film strength and gas barrier properties.

The method of stretching the polyamide film (unstretched) obtained by the above method is not particularly limited, and can be performed by a conventionally known industrial method.
For example, a simultaneous biaxial stretching method in which an unstretched film is simultaneously stretched longitudinally and laterally with a tenter simultaneous biaxial stretching machine,
A sequential biaxial stretching method in which an unstretched film 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,
There is a tubular stretching method in which a tubular film 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 stretch ratio of the stretched film varies depending on the intended use, but in the tenter-type biaxial stretching method and the tubular stretching method, it is usually preferably 1.5 to 4.5 times in both the longitudinal direction and the transverse direction. It is more preferable to be -4.0 times.
The stretching temperature is preferably 30 to 220 ° C, and more preferably 50 to 210 ° C.

It is desirable that the biaxially stretched film obtained by the above method is subsequently heat treated.
Dimensional stability at room temperature can be imparted by 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 raw material polyamide resin composition as the upper limit, preferably 150 ° C. or higher, and 180 to 220 ° C. It is more preferable that
The relaxation rate is preferably within 20% in the width direction, and more preferably 3 to 10%.
As a result, a biaxially stretched film having an arbitrary thermal shrinkage rate and good room temperature dimensional stability can be obtained.
The stretched film that has been sufficiently heat-set by the heat treatment operation can be cooled and wound up according to a conventional method.

Furthermore, the polyamide film may be subjected to surface treatment such as corona discharge treatment, plasma treatment, flame treatment, acid treatment, etc. in order to further improve the printability, lamination, and adhesive application.
The obtained biaxially stretched film is further subjected to secondary processing such as printing, laminating, pressure-sensitive adhesive application, heat sealing, etc. according to the intended use, and can be used in each intended use. .

[Polyamide laminated film]
The polyamide film of the present invention is excellent in slipperiness and printability and has a high utility value alone, but at least from the viewpoint of achieving both wettability and slipperiness of the laminated film,
A layer (x) comprising the polyamide film of the present invention;
A layer (y) comprising the component a,
The layer (x) and the layer (y) are in contact;
It is preferable that the layer (x) is a polyamide laminated film in which the outermost layer is disposed.

The polyamide film of the present invention can be added with more characteristics by laminating other thermoplastic resins.
Specifically, a thermoplastic resin layer can be laminated on at least one side of the polyamide film of the present invention to be used as a laminated film.

  Examples of laminated thermoplastic resins include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), 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 Polyolefin resin such as copolymer (EEA) and acrylic , 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 ] An acid anhydride group such as -5-heptene-2,3-dicarboxylic acid anhydride, and a functional group such as an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid The above-mentioned polyolefin resin, polybutylene terephthalate (PBT), polyethylene Terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), liquid crystal polyester (LCP), polylactic acid ( PLA), polyester resins such as polyglycolic acid (PGA), polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polyphenylene Polythioether resins such as sulfide (PPS) and polythioether sulfone (PTES), polyketone resins such as polyether ether ketone (PEEK) and polyallyl ether ketone (PAEK), polyacrylonitrile ( PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer ( MBS) and other polynitrile resins, polymethyl methacrylate (PMMA), polymethacrylate resins such as polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), Polyvinyl chloride (PVC), polyvinyl chloride such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resin such as cellulose acetate and cellulose butyrate, polycarbonate such as polycarbonate (PC) Resin, thermoplastic polyimide (PI), polyamideimide (PAI), polyimideimide resin such as polyetherimide, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), Polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / fluorination Fluorine resins such as vinylidene copolymers (TFE / HFP / VDF, THV), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymers (PFA), thermoplastic polyurethane resins, polyurethane elastomers Chromatography, polyester elastomer, polyamide elastomer, and the like.

  It is also possible to laminate the component a and the component b, and it is preferable to laminate the component a from the viewpoint of economy, and the polymetaxylylene adipamide (polyamide) from the viewpoint of balance of polyamide film strength and gas barrier properties. It is preferable to laminate MXD6) and ethylene / vinyl acetate copolymer saponified product (EVOH).

In the laminated film, the layer made of the raw material polyamide resin composition is preferably arranged in at least one outermost layer, and the laminating method is not particularly limited. For example, a coextrusion method, an extrusion laminating method, Examples include a dry laminating method.
The coextrusion method is a method of coextruding the raw material polyamide resin composition and another thermoplastic resin, and examples thereof include coextrusion sheet molding, coextrusion casting film molding, and coextrusion inflation film molding.
In the extrusion laminating method, the anchor coating agent is applied to the polyamide film of the present invention and a base material such as a thermoplastic resin, respectively, and after drying, the thermoplastic resin is melt-extruded while being cooled and pressed between rolls. In this method, a laminate film is obtained by pressure bonding.
In the dry laminating method, a known adhesive such as an organic titanium compound, an isocyanate compound, a polyester compound, or a polyurethane compound is applied to the polyamide film of the present invention, dried, and then laminated to a base material such as a thermoplastic resin. This is a method for obtaining a film.
The film after lamination can be increased in adhesive strength by aging.
The method of laminating by the coextrusion method together with the polyamide resin composition and the adhesive resin of the present invention is preferable because it does not require a surface treatment step such as an anchor coating agent or a known adhesive and is environmentally friendly and low cost.

The thickness of the polyamide film of the present invention may be appropriately determined depending on the use, and is not particularly limited, but in the case of a polyamide single-layer film in consideration of the strength, transparency and bending fatigue resistance of the obtained polyamide film, the thickness is 5 to 100 μm, more preferably 10 to 80 μm, and further preferably 10 to 60 μm.
In the case of the polyamide laminated film of the present invention, the thickness is preferably 5 to 200 μm, and preferably 10 to 150 μm, from the balance of strength, gas barrier properties, bending fatigue resistance, transparency and the like of the obtained film. More preferably, it is 12-100 micrometers.

  In the case of a polyamide laminated film composed of at least two layers including a layer (x) composed of the raw material polyamide resin composition and a layer (y) composed of the component a, the thickness ratio of the layer (x) to the total thickness Is preferably 5 to 40%, more preferably 10 to 35%. The thickness ratio of the layer (y) is preferably 60 to 95%, more preferably 65 to 90%.

  Moreover, it is desirable to provide a sealant layer in the obtained polyamide film or polyamide laminated film from the viewpoint of imparting heat sealability. The material used for the sealant layer may be any resin that can be heat-sealed, and generally includes polyolefin resins, polyester resins, and the like, and it is preferable to use polyolefin resins. 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 Polyester (A-PET) etc. are mentioned.

  In the present invention, “under high humidity” means that an atmosphere having a relative humidity (RH) of 50% is in a normal state and an atmosphere state having a higher relative humidity (RH) is present. RH) is in an atmospheric state exceeding 65%.

  The polyamide film according to the present invention preferably has a static friction coefficient of 1.0 or less, measured in an atmosphere of 23 ° C. and 90% relative humidity (RH) in accordance with ASTM D-1894, and 0.9 or less. It is more preferable that

  The present invention will be described below with reference to examples and comparative examples, but is not limited to the following examples. Various evaluation methods and raw materials used are shown below.

[Sliding]
At 23 ° C., relative humidity (RH) 50%, and 23 ° C., relative humidity (RH) 90%, the coefficient of static friction between the film surfaces was measured five times according to ASTM D-1894, and the average value was obtained. . When the coefficient of static friction at 23 ° C. and relative humidity (RH) 90% was 1.0 or less, it was judged that the slipperiness under high humidity was excellent.
[Tensile modulus]
The tensile elastic modulus of the film was measured with a universal material testing machine (Tensilon UTM III-200 manufactured by Orientec Co., Ltd.) according to ASTM D-882.
[Printability]
The wetting index was measured according to JIS K-6768.
[transparency]
According to ASTM D-1003, the haze value was measured using a direct reading haze computer (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP).
[Continuous productivity]
Using the raw material resin composition, it is melted at an extrusion temperature of 280 ° C. in a 40 mmφ extruder equipped with a circular die, and taken off while being cooled with water at 20 ° C., and an unstretched film is continuously formed. Manufactured. The operation was continued until the occurrence of eye grease with accumulated polymer degradation products and additive aggregates was observed at the circular die lip mouth.

[Raw materials used]
Component a
(A-1) Polyamide 6 (polymer comprising units derived from caprolactam): UBE NYLON 1022B (Saturated water absorption at 23 ° C. in water: 10.8% by mass, relative viscosity: 3.35) manufactured by Ube Industries, Ltd. )

Component b
(B-1) Polyamide MXD6 (polymer composed of units derived from m-xylylenediamine and units derived from adipic acid): MX-nylon 6011 (bending elastic modulus: 4) manufactured by Mitsubishi Gas Chemical Co., Ltd. 400 MPa, relative viscosity: 2.65)
(B-2) Polyamide 6T / 6I (a copolymer composed of units derived from 1,6-hexanediamine and units derived from terephthalic acid and isophthalic acid): manufactured by Mitsui DuPont Polychemical Co., Ltd. PA3426 (flexural modulus: 3,300 MPa, relative viscosity: 1.95)
(B-3) Polyamide 610 (polymer comprising units derived from 1,6-hexanediamine and units derived from sebacic acid): manufactured by Toray Industries, Inc., Amilan CM2001 (flexural modulus: 2,000 MPa, Relative viscosity: 2.5)

Component B
(B-1) Silica surface-treated with organopolysiloxane:
Mizusawa Chemical Industries, Ltd., Mizukasil PM-363DS, specific surface area 300 m ² / g, average particle size 4.0 μm,
Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone KF-96 100CS, molecular weight 6,000 g / mol, kinematic viscosity: 100 cSt)
Treatment amount: 10 parts by mass with respect to 100 parts by mass of silica.
(B-2) Silica surface-treated with organopolysiloxane:
Mizusawa Chemical Co., Ltd., Mizukasil C-102DS, specific surface area 20 m ² / g, average particle size 3.0 μm,
Dimethylpolysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Silicone KF-96 100CS, molecular weight 6,000 g / mol, kinematic viscosity: 100 cSt)
Treatment amount: 5 parts by mass with respect to 100 parts by mass of silica.
In addition, the said specific surface area and average particle diameter in a silica were measured with the following method, respectively.
[Specific surface area]
Based on JIS K-1150, it measured by the BET method from the adsorption amount of nitrogen.
[Average particle size]
The volume average particle size was measured by a particle size distribution measuring apparatus (manufactured by Beckman Coulter, Multisizer 4) by the Coulter counter method.

Component C
(C-1) N, N′-ethylenebisstearic acid amide:
NIPPON CHEMICAL CO., LTD., SLIPAX E, 18 carbon atoms of fatty acid
(C-2) N, N′-ethylenebisbehenamide:
NIPPON CHEMICAL CO., LTD., SLIPAX B, 20 carbon atoms of fatty acid
(C-3) N, N′-ethylenebislauric acid amide:
NIPPON CHEMICAL CO., LTD., SLIPAX L, 12 carbon atoms of fatty acid

Component D (other inorganic fillers)
(D-1) Silica:
Mizusawa Chemical Industry Co., Ltd., Mizukasil P-707, average particle size: 3.5 μm, specific surface area 260 m ² / g
(D-2) Silica surface-treated with γ-aminopropyltriethoxysilane:
Mizusawa Chemical Co., Ltd., Mizukasil C-402, average particle size: 3.5 μm, specific surface area 260 m ² / g

Example 1
For the total amount of (a-1) 90 parts by mass and (b-1) 10 parts by mass,
0.15 parts by mass of (B-1), 0.12 parts by mass of (C-1),
A raw material polyamide resin composition was obtained.
The raw material polyamide resin composition is introduced into a 40 mmφ single-shaft full flight screw extruder equipped with a circular die, melted at an extrusion temperature of 270 ° C., and taken up while being cooled with water at 20 ° C. A polyamide 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 subjected to heat setting treatment 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.

Examples 2-3
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the blending amount of (B-1) in Example 1 was changed to the amount shown in Table 1.

Example 4
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) was changed to (B-2) in Example 1.

Examples 5-6
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the blending amounts of (a-1) and (b-1) were changed to the amounts shown in Table 1 in Example 1.

Example 7
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (b-1) was changed to (b-2) in Example 1.

Examples 8-9
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the blending amount of (C-1) in Example 1 was changed to the amount shown in Table 1.

Example 10
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (C-1) was changed to (C-2) in Example 1.

Comparative Example 1
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) was not used in Example 1.

Comparative Examples 2-3
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that the blending amount of (B-1) in Example 1 was changed to the amount shown in Table 1.

Comparative Example 4
A biaxially stretched polyamide film was obtained in the same manner as in Example 1, except that (B-1) was changed to (D-1) in Example 1.

Comparative Example 5
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (B-1) was changed to (D-2) in Example 1.

Comparative Example 6
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (b-1) was not used.

Comparative Examples 7-8
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the blending amounts of (a-1) and (b-1) were changed to the amounts shown in Table 1 in Example 1.

Comparative Example 9
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (b-1) was changed to (b-3) in Example 1.

Comparative Example 10
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (C-1) was not used.

Comparative Examples 11-12
In Example 1, a biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that the amount of (C-1) was changed to the amount shown in Table 1.

Comparative Example 13
A biaxially stretched polyamide film was obtained in the same manner as in Example 1 except that (C-1) was changed to (C-3) in Example 1.

  Table 1 shows the results of investigating the physical property measurement results and continuous productivity of the biaxially stretched polyamide films obtained in Examples 1 to 10 and Comparative Examples 1 to 13.

Example 11
In a 40 mmφ extruder equipped with a circular three-layer die, the raw material polyamide resin composition (resin component of layer (x)) used in Example 1 and (a-1) (resin component of layer (y)) Polyamide laminated film in which each is melted separately at an extrusion temperature of 270 ° C., and taken up while being cooled with water at 20 ° C., and three layers having a layer configuration of (x) / (y) / (x) are directly laminated. Got.

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.
Release both ends of the film from the clip, trim the ears and wind up,
A polyamide laminated biaxially stretched film of (x) / (y) / (x) = 2 μm / 11 μm / 2 μm was obtained. Table 2 shows the physical property measurement results of the polyamide laminated biaxially stretched film.

Comparative Example 14
In Example 11, the same method as in Example 1 except that the raw material polyamide resin composition used in Example 1 was changed to the raw material polyamide resin composition (resin component of layer (x)) used in Comparative Example 6. (X) / (y) / (x) = 2 μm / 11 μm / 2 μm polyamide laminated biaxially stretched film was obtained. Table 2 shows the physical property measurement results of the polyamide laminated biaxially stretched film.

  From the results of Tables 1 and 2, it is judged that a tensile modulus of 3,000 MPa or less is suitable for soft packaging, and a wetting index of 36 mN / m or more is excellent in printability. In the case where the generation of eye grease with accumulated aggregates of additives was not observed, it was judged that the continuous productivity was excellent.

The polyamide resin composition of the present invention comprises ASTM D-790 in component a (polyamide resin having a saturated water absorption rate of 23% at 80 ° C. in water) and component b (23 ° C., relative humidity (RH) 50%). Inorganic filler (component B) in which inorganic filler particles are surface-treated with organopolysiloxane for polyamide resin (component A) with a flexural modulus measured according to And a specific amount of a bisamide compound (component C) comprising a fatty acid having 14 or more carbon atoms and a diamine,
The polyamide film comprising the polyamide resin composition of the present invention can be continuously produced, is suitable for flexible packaging, has excellent slipperiness and printability,
In particular, to provide excellent slipperiness at high humidity with a static friction coefficient of 1.0 or less measured and adjusted in an atmosphere of 23 ° C. and relative humidity (RH) 90%, which could not be realized until now. Can do.

Claims (8)

A polyamide resin composition comprising a polyamide resin (component A), an inorganic filler (component B), and a bisamide compound (component C),
Component A consists of 60 to 98 parts by mass of component a and 40 to 2 parts by mass of component b,
The component a is a polyamide resin having a saturated water absorption rate of 23% by weight in water of 8.0% by mass or more,
The component b is a polyamide resin having a flexural modulus of 3,000 MPa or more measured in accordance with ASTM D-790 at 23 ° C. and a relative humidity (RH) of 50%.
Component B is obtained by subjecting inorganic filler particles to surface treatment with organosiloxane,
The component C is obtained by reacting a diamine with a fatty acid having 14 or more carbon atoms,
The content of the components A, B and C is
For 100 parts by mass of component A,
Component B is 0.01 to 0.4 parts by mass,
The polyamide resin composition whose said component C is 0.02-25 mass parts. The inorganic filler particles are silica;
The polyamide resin composition according to claim 1, wherein 100 parts by mass of the inorganic filler particles are surface-treated with 0.5 to 15 parts by mass of the organosiloxane.   The polyamide resin composition according to claim 1 or 2, wherein the content of units derived from caprolactam in component a is 50 mol% or more with respect to 100 mol% of all polymerized units of component a.   The component a is at least one selected from the group consisting of polyamide 6, polyamide 6/66, polyamide 6/12, polyamide 6 / IPDT, and polyamide 6/66/12. The polyamide resin composition as described. The component b is
units derived from m-xylylenediamine and / or units derived from p-xylenediamine;
A polymer comprising a unit derived from an aliphatic dicarboxylic acid having 6 to 12 carbon atoms (component b-1),
And / or
Units derived from terephthalic acid and / or units derived from isophthalic acid;
Polymer composed of units derived from aliphatic diamine having 6 to 12 carbon atoms (component b-2)
The polyamide resin composition according to any one of claims 1 to 4.   A polyamide film comprising the polyamide resin composition according to claim 1.   The polyamide film according to claim 6, which is a biaxially stretched polyamide film. at least,
A layer (x) comprising the polyamide film according to claim 6 or 7,
A layer (y) comprising the component a,
The layer (x) and the layer (y) are in contact;
A polyamide laminated film in which the layer (x) is disposed in the outermost layer.