JP7322458B2 - Easy adhesion polyamide film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a biaxially stretched polyamide film having excellent pinhole resistance and adhesiveness. In particular, the present invention relates to a biaxially stretched polyamide film having excellent water-resistant adhesive strength with a sealant film.

Biaxially stretched polyamide films are excellent in tensile strength, bending strength, pinhole resistance, oil resistance, oxygen gas barrier properties, etc., and are therefore used as packaging materials, especially food packaging materials.

Biaxially oriented polyamide film is usually laminated with heat-sealable polyolefin films (also called sealant films) such as polyethylene and polypropylene, and heat-sealed at the edges of the bag to be used as a packaging bag. used. Biaxially oriented polyamide films are widely used as food packaging materials.

However, when a laminated film of biaxially oriented polyamide film and sealant film is used for liquid soup bags and water bags, the adhesive strength between the laminated films (also called lamination strength) is weak and the laminated film peels off. There was a problem. In particular, after hot water treatment at high temperature such as retort, water permeates between the laminated films, resulting in an extremely low lamination strength between the biaxially oriented polyamide film and the sealant film.

As a method for improving the lamination strength, a method has been proposed in which the surface of the film is coated during the film manufacturing process to increase the adhesive strength (see Patent Document 1). However, this method has the problem of poor productivity and high production costs. Furthermore, the coating causes problems such as blocking, streaks, and scratches. Therefore, there has been a demand for a biaxially oriented polyamide film that has high lamination strength even without coating.

Therefore, a laminated polyamide film has been proposed in which an unstretched sheet obtained by coextrusion of a layer containing copolyamide as a surface layer is biaxially stretched (see Patent Document 2). However, although this method improves the lamination strength, it is necessary to coat the film surface in the process of producing the film in order to obtain a strong waterproof lamination strength.

On the other hand, a method for producing a biaxially stretched polyamide film made of a polyamide 6/66 copolymer and having improved sequential biaxial stretchability has been proposed (see Patent Document 3).
Also, a method for producing a biaxially stretched polyamide 6/66 copolymer film with good thickness accuracy by a tubular method has been proposed (see Patent Document 4).
Biaxially oriented polyamide films made of these polyamide 6/66 copolymers have a lower melting point than polyamide 6 and polyamide 66, so they have poor heat resistance and dimensional stability at high temperatures, and are used for boiling and retorting. Not suitable for films for packaging bags.

A five-layer biaxially oriented polyamide film is proposed in which a layer containing polyamide 6 as a main component, a layer composed of polyamide 6 and polyamide 6/66, and a barrier layer containing a saponified ethylene-vinyl acetate copolymer are laminated and extruded. (see Patent Document 5). However, since it includes a barrier layer containing saponified ethylene-vinyl acetate copolymer, it is not possible to recover and reuse the film at the clip gripping portion in the tenter. It has also been proposed to use a layer containing poly-meta-xylylene adipamide as a main component as a barrier layer (see Patent Document 6). However, in this case, there is a problem that the impact resistance and pinhole resistance of the film are deteriorated.

Patent 04660866 Patent 04178814 Japanese Examined Patent Publication No. 57-8647 Tokuho 6-37081 Patent 05068084 Patent 05383563

An object of the present invention is to solve the above-mentioned problems of conventional biaxially stretched polyamide films, and to provide a biaxially stretched polyamide film which is excellent in pinhole resistance and adhesiveness, particularly in waterproof lamination strength, at a low cost. It is in.

As a result of intensive studies, the present inventors have found that the problem can be solved by a biaxially oriented polyamide film in which an easy-adhesion layer mainly composed of a polyamide 6 copolymer is laminated on a base layer composed mainly of polyamide 6 containing a polyamide elastomer. I found
The present invention consists of the following configurations.
[1] A substrate layer (A layer) containing 98 to 80% by mass of a polyamide 6 resin and 2 to 20% by mass of a polyamide-based elastomer is coated on at least one side with a copolymer component having a ratio of 3 to 35 in the copolymer. An easy-adhesive polyamide film characterized by laminating an easy-adhesion layer (layer B) containing 60 to 100% by mass of polyamide 6 copolymer and 0 to 40% by mass of polyamide 6.
[2] The laminated stretched polyamide film of [1], wherein the A layer and the B layer are laminated in the order of A layer/B layer or B layer/A layer/B layer.
[3] The laminated stretched polyamide film of [1] or [2], wherein the polyamide 6 copolymer is a polyamide 6/66 copolymer.
[4] The laminated stretched polyamide film of [3], wherein the layer A contains 0.5 to 30% by mass of a polyamide 6/66 copolymer.
[5] The laminated stretched polyamide film of [1] or [2], wherein the polyamide 6 copolymer is a polyamide 6/12 copolymer.
[6] The laminated stretched polyamide film of [5], wherein the layer A contains 0.5 to 30% by mass of a polyamide 6/12 copolymer.
[7] The laminated stretched polyamide film has a thickness of 5 to 30 μm, the layer A has a thickness of 4.5 μm or more, and the layer B has a thickness of 0.5 μm or more [1] to [6]. ], the laminated stretched polyamide film according to any one of
[8] The laminated stretched polyamide film according to any one of [1] to [7], which has a waterproof lamination strength of 2.0 N/15 mm or more.

The easy-adhesive polyamide film of the present invention has excellent impact strength, pinhole resistance, gas barrier properties, etc., which are possessed by biaxially oriented polyamide films, and also has strong water-resistant lamination strength. It is effective in preventing the packaging bag from breaking due to shock or vibration during transportation.
In addition, the laminated stretched polyamide film of the present invention has the advantages of being highly productive and economical because the coating process can be omitted, and having few defects such as scratches. Furthermore, the easily adhesive polyamide film of the present invention has the advantage of being hygienic because it is not laminated with a coating agent.

The easily adhesive polyamide film of the present invention will be described in detail below.
The laminated stretched polyamide film of the present invention comprises a base layer (layer A) containing 98 to 80% by mass of a polyamide 6 resin and 2 to 20% by mass of a polyamide elastomer, and on at least one surface of the base layer (layer A), a copolymer component in the copolymer. 60 to 100% by mass of a polyamide 6 copolymer having a ratio of 3 to 35% by mass and an easy-adhesion layer (layer B) containing 0 to 40% by mass of polyamide 6 is laminated.
Examples of the laminated structure of the laminated stretched polyamide film of the present invention include a structure in which the layers are laminated in the order of A layer/B layer or B layer/A layer/B layer.

The total thickness of the laminated stretched polyamide film of the present invention is 5-30 μm. When the total thickness of the laminated stretched polyamide film is thicker than 30 μm, the performance is saturated in terms of strength. In addition, the flexibility of a packaging bag obtained by laminating with a sealant is deteriorated.

The thickness of the substrate layer (layer A) of the laminated stretched polyamide film of the present invention is 4.5 μm or more. If the thickness of the base material layer (layer A) is less than 4.5 μm, the film as a whole is too soft to be processed by a printing machine or a bag making machine. The laminate structure of the laminated stretched polyamide film of the present invention includes, in addition to the structure laminated in the order of A layer/B layer or B layer/A layer/B layer, B layer/A layer/B layer/A layer /B layers may be stacked in this order, or a multi-layer structure may be used. In this case, the total thickness of the A layers is preferably 4.5 μm or more.

The thickness of the easy-adhesion layer (B layer) of the laminated stretched polyamide film of the present invention is 0.5 μm or more. If the thickness of the B layer is less than 0.5 μm, the waterproof laminate strength, which is the object of the present invention, cannot be obtained. There is no particular upper limit for the thickness of the B layer. However, if the thickness of the layer B exceeds 5 μm, the water-resistant lamination strength becomes saturated, so the thickness is preferably 5 μm or less. Here, the easy adhesion layer (B layer) that requires a thickness of 0.5 μm or more is the thickness of the B layer on the side to be laminated with the sealant. In the case of a structure laminated in the order of B layer / A layer / B layer or a structure laminated in the order of B layer / A layer / B layer / A layer / B layer, other than the layer that becomes the surface to be laminated with the sealant The layer thickness can be less than 0.5 μm.

<Base material layer (A layer)>
The base layer (A layer) in the present invention is a polyamide resin composition containing 97.5 to 80% by mass of polyamide 6 resin and 2.5 to 20% by mass of polyamide elastomer.
The base layer (A layer) in the present invention contains 2.5 to 20% by mass of a polyamide elastomer, so that it has a structure in which the polyamide elastomer as a pinhole resistant material is dispersed, and has excellent bending pinhole resistance. In particular, it is possible to obtain a laminated stretched polyamide film having good flex pinhole resistance in a low-temperature environment.
The base material layer (A layer) in the present invention has a polyamide 6 resin content of 97.5 to 80% by mass, so that a laminated stretched polyamide film having good mechanical strength such as impact strength can be obtained. .

Examples of the polyamide-based elastomer used for the base material layer (layer A) in the present invention include polyamide-based block copolymers composed of a hard segment composed of a polyamide component and a soft segment composed of a polyoxyalkylene glycol component. . The polyamide component of the hard segment is selected from the group consisting of (1) lactams, (2) aminoaliphatic carboxylic acids, (3) aliphatic diamines and aliphatic dicarboxylic acids, or (4) aliphatic diamines and aromatic dicarboxylic acids. be done. Specifically, (1) ω-lauryllactam, ε-caprolactam, (2) aminoheptanoic acid, (3) hexamethylenediamine, nonanediamine and adipic acid, sebacic acid, (4) hexamethylenediamine, nonanediamine and terephthalic acid , and isophthalic acid. Examples of polyoxyalkylene glycols constituting soft segments of polyamide-based block copolymers include polyoxytetramethylene glycol, polyoxyethylene glycol, and polyoxy-1,2-propylene glycol. A polyamide elastomer having a hard segment of polyamide 6 or polyamide 12 and a soft segment of polyoxytetramethylene glycol is particularly preferable because it has a high effect of improving bending pinhole resistance.

The melting point of the polyamide-based elastomer in the present invention is determined by the type and ratio of the hard segment composed of the polyamide component and the soft segment composed of the polyoxyalkylene glycol component. things are used.

In the present invention, by using the polyamide-based elastomer as a constituent component of the base layer of the laminated stretched polyamide film, the bending pinhole resistance of the laminated stretched polyamide film, particularly the bending pinhole resistance in a low temperature environment, can be improved.
The lower limit of the content of the polyamide-based elastomer in the polyamide resin composition of the base material layer is 2.5% by mass. As a result, a laminated stretched polyamide film having good flex pinhole resistance can be obtained.
The upper limit of the content of the polyamide-based elastomer in the polyamide resin composition of the base material layer is 20% by mass. As a result, a laminated stretched polyamide film having good bending pinhole resistance can be obtained while maintaining other mechanical properties and transparency.

The polyamide resin composition that constitutes the A layer is a mixture of virgin raw material polyamide 6 and a polyamide-based elastomer, as well as non-standard films and cut scraps (edge trim) generated when manufacturing laminated stretched polyamide films. may be added to the virgin raw material as a recycled resin.

The polyamide resin composition constituting the layer A preferably contains 0.01 to 0.3% by mass of an antioxidant. If the content of the antioxidant exceeds the above range, whitening due to deposition on the surface of the laminated stretched polyamide film, etc., and poor adhesion during lamination with polyethylene and polypropylene sealants will occur. When recycled raw materials such as waste materials and recycled resins are used as the polyamide resin composition of (1), poor film-forming operability may occur due to thermal deterioration of the recovered recycled raw materials.

Phenolic antioxidants are preferred as antioxidants. The phenolic antioxidant is preferably a fully hindered phenolic compound or a partially hindered phenolic compound. For example, tetrakis-[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)propionate]methane, stearyl-β-(3,5-di-t-butyl-4-hydroxy phenyl)propionate, 3,9-bis[1,1-dimethyl-2-[β-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]2,4,8,10- tetraoxaspiro[5,5]undecane and the like.

By including the phenolic antioxidant in the polyamide resin composition of the layer A, the workability of forming the laminated stretched polyamide film is improved. In particular, in a mixed recycled raw material system using film scraps, recycled resin, etc., thermal deterioration due to recovery and recycling of the thermoplastic elastomer is likely to occur, and film production operation failures due to this occur. The increase in production costs and the decrease in the amount of recovered and recycled raw materials used lead to an increase in the use of virgin raw materials, which tends to lead to an increase in production costs. On the other hand, by including an antioxidant in the polyamide resin composition of the A layer of the stretched polyamide film containing recycled raw materials, the thermal deterioration of various polymers including thermoplastic elastomers can be suppressed. , to achieve stable film production operability. Therefore, according to the present invention, it is possible to reduce the production cost by improving the operability and reducing the raw material cost by increasing the amount of recovered and recycled raw material used.

<Easy adhesion layer (B layer)>
The easy-adhesion layer (B layer) of the laminated stretched polyamide film of the present invention contains 60 to 100 mass % of a polyamide 6 copolymer having a copolymer content of 3 to 35 mass % in the copolymer.
If the content of the polyamide 6 copolymer in the easy-adhesion layer (B layer) is less than 60% by mass, sufficient water-resistant laminate strength cannot be obtained.
The ratio of the copolymer component in the polyamide 6 copolymer is 3 to 35% by mass.
If the ratio of the copolymer component is less than 3% by mass, sufficient water-resistant laminate strength cannot be obtained.
If the ratio of the copolymer component in the copolymer is more than 35% by mass, it may become difficult to handle when supplying raw materials.
The melting point of the polyamide 6 copolymer is preferably 170 to 220°C. It is more preferably 175 to 215°C, still more preferably 180 to 210°C. If the melting point of the polyamide 6 copolymer is higher than 215°C, sufficient waterproof adhesion may not be obtained. When the melting point of the polyamide 6 copolymer is lower than 170°C, it may become difficult to handle when supplying raw materials.

The polyamide 6 copolymer used for the easy-adhesion layer (B layer) is obtained by copolymerizing ε-caprolactam or aminocaproic acid with a copolymer component at a ratio of 3 to 35% by mass. Here, the copolymerization ratio is mass % after removing the monomer remaining after copolymerization with hot water or the like.
The component for copolymerization with ε-caprolactam can be obtained, for example, by copolymerizing a lactam other than ε-caprolactam or a salt of an amino acid or dicarboxylic acid other than aminocaproic acid and a diamine. Examples of monomers to be copolymerized with ε-caprolactam in the polymerization of polyamide 6 copolymer include undecanelactam, lauryllactam, aminoundecanoic acid, aminolauric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, and terephthalic acid. , isophthalic acid, hexamethylenediamine, nonanediamine, decanediamine, methylpentanediamine, metaxylylenediamine, trimethylhexamethylenediamine, and the like.
Examples of the polyamide 6 copolymer include polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/6T copolymer, polyamide 6/610 copolymer, and polyamide 6/6I copolymer. , polyamide 6/9T copolymer, polyamide 6/6I copolymer, polyamide 6/11 copolymer, and the like.

The polyamide 6/66 copolymer used for the easy-adhesion layer (B layer) is obtained by a method of polymerizing ε-caprolactam and hexamethylenediammonium adipate.
Commercially available products such as Ultramid C3301 (manufactured by BASF) and Nylon 5023B (manufactured by Ube Industries, Ltd.) can also be used.
The polyamide 6/66 copolymer that may be contained in the A layer in an amount of 0.5 to 30% by mass may also be the one described above.

The copolymerization ratio of polyamide 6 and polyamide 66 in the polyamide 6/66 copolymer is 3 to 35 mass % of polyamide 66 in the polyamide 6/66 copolymer. Preferably, it is 5 to 30% by mass. More preferably, it is 5 to 25% by mass.
When the proportion of polyamide 66 in the polyamide 6/66 copolymer is less than 3% by mass, the easy adhesion, which is the subject of the present invention, is not exhibited.
If the proportion of polyamide 66 in the polyamide 6/66 copolymer is more than 35% by mass, the copolymer may have low crystallinity and may be difficult to handle.
The polyamide 6/66 copolymer preferably has a relative viscosity of 1.8 to 4.5, more preferably 2.6 to 3.2.

The polyamide 6/12 copolymer used for the easy-adhesion layer (B layer) is obtained by a method of polymerizing ε-caprolactam and ω-lauryllactam.
Commercially available products such as nylon resin 7024B (manufactured by Ube Industries, Ltd.) can also be used.
The polyamide 6/12 copolymer that may be contained in the A layer in an amount of 0.5 to 30% by mass may also be the one described above.

As for the copolymerization ratio of polyamide 6 and polyamide 12 in the polyamide 6/12 copolymer, the ratio of polyamide 12 in the polyamide 6/12 copolymer is 3 to 35% by mass. Preferably, it is 5 to 30% by mass. More preferably, it is 5 to 25% by mass.
When the proportion of polyamide 12 in the polyamide 6/12 copolymer is less than 3% by mass, the easy adhesion, which is the subject of the present invention, is not exhibited.
If the proportion of polyamide 12 in the polyamide 6/12 copolymer is more than 35% by mass, the copolymer may have low crystallinity and may be difficult to handle.
The polyamide 6/12 copolymer preferably has a relative viscosity of 1.8 to 4.5, more preferably 2.5 to 4.0.

An important point in the present invention is that by laminating an easy-adhesion layer (B layer) containing a polyamide 6 copolymer on the side of the substrate layer (A layer) to be laminated with the sealant, the surface to be laminated with the sealant is The point is that the degree of crystallinity is lowered.

As a method for laminating the easy-adhesion layer (B layer) containing the polyamide copolymer on the substrate layer (A layer), a coextrusion method using a feed block, a multi-manifold, or the like is preferable. Other than the coextrusion method, a dry lamination method, an extrusion lamination method, or the like can also be selected.

When laminating by coextrusion, it is desirable to select the relative viscosities of the polyamides used for the A layer and the B layer so that the difference in melt viscosity between the A layer and the B layer is small.

The stretching method for obtaining the laminated stretched polyamide film of the present invention may be either a sequential biaxial stretching method or a simultaneous biaxial stretching method. The sequential biaxial stretching method is preferable because the film-forming speed can be increased, which is advantageous in terms of production cost. A uniaxially stretched polyamide film having good lamination strength can be obtained even if the film is uniaxially stretched by a uniaxial stretching method. However, the biaxially oriented polyamide film has better impact resistance and pinhole resistance.
As an apparatus, a usual sequential biaxial stretching apparatus is used. The conditions for production include an extrusion temperature of 200° C. to 300° C., a stretching temperature in the machine direction (sometimes abbreviated as MD), which is the flow method of the device, of 50 to 100° C., and a stretching ratio in the machine direction of 2 to 5 times. It is preferable that the stretching temperature in the width direction (sometimes abbreviated as TD) of the device is 120 to 200°C, the stretching ratio in the width direction is 3 to 5 times, and the heat setting temperature is 200°C to 230°C.

As for the stretching conditions for the laminated stretched polyamide film of the present invention, it is preferably stretched 2.8 times or more in both the machine direction and the width direction, and more preferably 3.2 times or more in the width direction. Moreover, the higher the heat setting temperature, the higher the water resistant lamination strength tends to be obtained, which is preferable. If the heat setting temperature is lower than 200°C, sufficient water resistant laminate strength and thermal dimensional stability may not be obtained.

A coating layer may be provided between the layer containing the polyamide copolymer and the sealant layer to further increase the adhesive strength with the sealant. In this case, the coating agent is preferably water-resistant in order to increase the strength of the water-resistant laminate. In addition, when it is desired to increase the adhesive strength with the sealant, corona treatment, flame treatment, or the like may be performed.

The easy-adhesion layer (B layer) and/or the base layer (A layer) of the laminated stretched polyamide film of the present invention may contain a lubricant, an antiblocking agent, and a heat stabilizer within a range that does not impede properties such as water-resistant laminate strength. , antioxidants, antistatic agents, light stabilizers, impact modifiers, and other additives.
In particular, it is preferable to add an organic lubricant such as ethylenebisstearic acid amide (EBS), which exhibits the effect of lowering the surface energy, because the film becomes more slippery. Moreover, it is preferable to add inorganic fine particles such as silica fine particles as an antiblocking agent.

The laminated stretched polyamide film of the present invention preferably has a haze value of 5.0% or less, more preferably 4.0%, and still more preferably 2.5% or less. If the haze value exceeds 5.0%, the transparency deteriorates, and it is not preferable as a packaging material with a highly designed design that makes the most of the transparency.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples as long as the gist of the present invention is not exceeded.
In addition, evaluation of the film was performed based on the following measuring method. Unless otherwise specified, measurements were carried out in a measurement room at 23° C. and a relative humidity of 65%.

(1) Film thickness Divide the film into 10 equal parts in the width direction (TD) (for narrow films, divide the width so that the width that allows thickness measurement can be secured), and divide the film lengthwise into 100 mm films. It is cut out in a layered manner and conditioned for 2 hours or more in an environment with a temperature of 23° C. and a relative humidity of 65%.
The center thickness of each sample was measured using a tester industry thickness gauge, and the average value was taken as the thickness.
The thickness of the base layer (A layer) and the easy-adhesion layer (B layer) is the total thickness of the laminated stretched polyamide film measured by the above method, and the discharge amount of the base layer (A layer) and the easy-adhesion layer (B layer). ) was measured, and the thicknesses of the substrate layer (A layer) and the easily adhesive layer (B layer) were calculated based on the ratio of the ejection amounts.

(2) Heat Shrinkage Rate of Film Five films each having a size of 20 mm in width×250 mm in length were cut out from each of the machine direction (MD) and the width direction (TD) to obtain test specimens. Each test piece was provided with marking lines at intervals of 200 mm±2 mm around the center of the test piece. The interval between the marked lines of the test piece before heating was measured with an accuracy of 0.1 mm. The test piece was suspended in a hot air dryer (PHH-202, manufactured by Espec Co., Ltd.) without load, and heat-treated at 160° C. for 10 minutes. After removing the test piece from the constant temperature bath and cooling it to room temperature, the length and width were measured on the same part as the first measurement. The dimensional change rate of each test piece was calculated as a percentage of the initial dimensional change in the longitudinal and transverse directions. The dimensional change rate in each direction was the average of the measured values in that direction.

(3) Film impact strength A film impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to measure 10 times under an environment of a temperature of 23°C and a relative humidity of 65%, and the average value was evaluated. A 1/2 inch diameter impact sphere was used. The unit used was J/15 μm, which is the intensity per 15 μm.

(4) Pinhole Resistance of Film Using a gelboflex tester BE1006 with a constant temperature bath manufactured by Tester Sangyo Co., Ltd., the number of pinholes was measured by the following method.
A polyester adhesive [a mixture of TM-569 (product name) and CAT-10L (product name) manufactured by Toyo-Morton Co., Ltd. in a mass ratio of 7.2/1 (solid content concentration 23%)] was applied to the film. After coating so that the resin solid content after drying is 3.2 g/m ² , a linear low-density polyethylene film (L-LDPE film: manufactured by Toyobo Co., Ltd., RIX (registered trademark) L4102) 40 μm is dry-laminated. , and 40° C. for 2 days to obtain a laminate film.

The resulting dry laminate film was cut into a size of 28.0 cm (11 inches) x 24.0 cm (9.4 inches), and the cut film was placed under conditions of a temperature of 23°C and a relative humidity of 50%. It was left to stand for 6 hours or longer for conditioning. After that, the rectangular test film was wound up to a diameter of 8.9 mm. Form into a 3.5 inch (cm) cylinder. Then, one end of the cylindrical film was fixed to the outer periphery of the disk-shaped fixed head of the Gelboflex tester, and the other end of the cylindrical film was opposed to the fixed head by 19.4 cm (7.6 inches). was fixed to the outer circumference of the disc-shaped movable head. The movable head is then rotated 440° while approaching the movable head 7.6 cm (3.5 inches) along the axes of both parallel and opposed heads in the direction of the fixed head, followed by 6.4 cm (6.4 cm) without rotation. 2.5 inches) straight ahead and then reverse the motions to return the moving head to the initial position for 1000 consecutive cycles at a rate of 40 cycles per minute. repeated. The run was done at 1°C. Afterwards, the number of pinholes in a 19.4 cm (7.6 inch) by 25.5 cm (11 inch) portion of the tested film, excluding the portions fixed to the periphery of the fixed and movable heads, was counted ( That is, the number of pinholes per 495 cm2 (77 square inches) was measured).

(5) Water resistant laminate strength (laminate strength under water adhesion conditions)
A laminate film prepared in the same manner as described in the description of evaluation of pinhole resistance was cut into strips of width 15 mm × length 200 mm, and one end of the laminate film was attached to a biaxially stretched polyamide film and a linear low-density polyethylene film. (manufactured by Shimadzu Corporation, Autograph), under the conditions of a temperature of 23 ° C., a relative humidity of 50%, a tensile speed of 200 mm / min, and a peeling angle of 90 °, the strip-shaped laminate film The lamination strength was measured three times while dropping water on the peeled interface with a dropper, and the average value was evaluated.

(6) Relative Viscosity of Raw Polyamide 0.25 g of polyamide was dissolved in 96% sulfuric acid in a 25 ml volumetric flask to a concentration of 1.0 g/dl, and the relative viscosity was measured at 20°C.
(7) Melting point of raw polyamide According to JIS K7121, using an SSC5200 differential scanning calorimeter manufactured by Seiko Instruments Inc., in a nitrogen atmosphere, sample weight: 10 mg, temperature rise start temperature: 30 ° C., temperature rise Speed: Measured at 20°C/min, and the endothermic peak temperature (Tmp) was determined as the melting point.

(Example 1-1)
Using a device consisting of two extruders and a co-extrusion T-die with a width of 380 mm, the layers are laminated in a layer A/B layer configuration, and the molten resin is extruded from the T-die into a sheet, which is then transferred to a cooling roll whose temperature is controlled at 20°C. A laminated unstretched sheet having a thickness of 200 μm was obtained by bringing them into close contact with each other.
The resin compositions of the A layer and the B layer are as follows.
Resin composition constituting layer A: Nylon 6 (manufactured by Toyobo Co., Ltd., relative viscosity 2.8, melting point 220 ° C.) 97 parts by mass, and polyamide elastomer in which nylon 12 is a hard segment and polytetramethylene glycol is a soft segment (PEBAX4033SA02 manufactured by Arkema) 3.0 parts by mass, 0.54 parts by mass of fine silica particles and 0.15 parts by mass of fatty acid amide.
Resin composition constituting layer B: 9 parts by mass of polyamide 6 (relative viscosity 2.8, melting point 220 ° C.) and polyamide 6/66 copolymer (ratio of polyamide 66 is 7% by mass, relative viscosity 2.8, melting point 198° C.) 91 parts by mass, 0.54 parts by mass of fine silica particles, and 0.15 parts by mass of fatty acid amide.
In addition, the used raw material was used after drying so that the moisture content might be 0.1 mass %.

The obtained laminated unstretched sheet was guided to a roll type stretching machine, stretched 1.7 times in the longitudinal direction at 80°C by utilizing the peripheral speed difference of the rolls, and then further stretched 1.85 times at 70°C. . Subsequently, this uniaxially stretched film is continuously guided to a tenter type stretching machine, preheated at 110°C, and then stretched in the width direction (MD) by 1.2 times at 120°C, 1.7 times at 130°C, and 2 times at 160°C. After stretching 0.0 times and heat-setting at 210° C., it is subjected to relaxation treatment of 3% at 210° C. and 2% at 185° C. Then, the surface of the easy-adhesive layer (B layer) is subjected to corona discharge treatment to form A layer. A laminated biaxially stretched polyamide film of 2 types and 3 layers laminated in the order of /B layer was obtained.
The thickness of the laminated stretched polyamide film was set so that the total thickness was 15 μm, the thickness of the substrate layer (A layer) was 12 μm, and the thickness of the easily adhesive layer (B layer) was 1.5 μm. The configuration and extruder output were adjusted.

(Example 1-2)
Polyamide 6, polyamide-based elastomer and polyamide 6/66 copolymer are blended at a mass ratio of 90/5/5 as a base layer (A layer) and melt extruded, and polyamide is used as an easy-adhesion layer (B layer). 6 and a polyamide 6/66 copolymer were melt extruded in a mass ratio of 15/85. A laminated biaxially stretched polyamide film was produced in the same manner as in Example 1-1 except for the above.

(Example 1-3)
A laminated biaxially oriented polyamide film was produced in the same manner as in Example 1-2, except that polyamide 6 and polyamide 6/66 copolymer were melt extruded at a mass ratio of 30/70 as an easy-adhesion layer (B layer).

(Example 1-4)
A laminated biaxially stretched polyamide film was produced in the same manner as in Example 1-2, except that polyamide 6 and polyamide 6/66 copolymer were melt extruded at a mass ratio of 40/60 as an easy-adhesion layer (B layer).

(Example 1-5)
Polyamide 6/66 copolymer with a higher copolymerization ratio of polyamide 66 instead of polyamide 6/66 copolymer (polyamide 66 ratio of 7% by mass, relative viscosity of 2.8, melting point of 198 ° C.) (polyamide 66 A laminated biaxially stretched polyamide film was produced in the same manner as in Example 1-2, except that a ratio of 25% by mass, a relative viscosity of 2.7, and a melting point of 187° C.) was blended at a mass ratio of 15/85.

(Comparative Example 1-1)
A laminated biaxially stretched polyamide film was produced in the same manner as in Example 1-2, except that 100% by mass of polyamide 6 was melt-extruded as the base layer (layer A).

(Comparative Example 1-2)
Laminated biaxially in the same manner as in Example 1-2 except that a mixture of polyamide 6 and polyamide 6/66 copolymer at a mass ratio of 50/50 was melt extruded as an easy adhesion layer (B layer). A stretched polyamide film was produced.

Table 1 shows the water resistant laminate strength and other physical properties of the biaxially oriented polyamide films produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 and 1-2.

As is clear from the results in Table 1, in the case of Examples 1-1 to 1-5 in which the easy-adhesion layer (B layer) contains 60% by mass or more of the 6/66 copolymer, sufficient water-resistant laminate strength was obtained. is obtained.
On the other hand, Comparative Example 1-1 has poor pinhole resistance because it does not contain a polyamide elastomer, and Comparative Example 1-2 has a low content of polyamide 6/66 copolymer in the easy-adhesion layer. Water resistant laminate strength cannot be obtained.

(Example 2-1)
Polyamide 6/66 copolymer (7% by mass of polyamide 66, relative viscosity 2.8, melting point 198 ° C.) instead of polyamide 6/12 copolymer (manufactured by Ube Industries, Ltd. 7024B: relative viscosity 2.6 A laminated biaxially stretched polyamide film was prepared in the same manner as in Example 1-1, except that the polymer was blended at a mass ratio of 9/91.

(Example 2-2)
Polyamide 6, polyamide-based elastomer and polyamide 6/12 copolymer are blended at a mass ratio of 90/5/5 as a base layer (A layer) and melt extruded, and polyamide is used as an easy-adhesion layer (B layer). 6 and a polyamide 6/polyamide 12 copolymer were melt-extruded so as to have a mass ratio of 15/85. A laminated biaxially stretched polyamide film was produced in the same manner as in Example 2-1 except for the above.

(Example 2-3)
A laminated biaxially stretched polyamide film was produced in the same manner as in Example 2-2, except that polyamide 6 and polyamide 6/12 copolymer were melt extruded at a mass ratio of 30/70 as an easy-adhesion layer (B layer).

(Example 2-4)
A laminated biaxially stretched polyamide film was produced in the same manner as in Example 2-2, except that polyamide 6 and polyamide 6/12 copolymer were melt extruded at a mass ratio of 40/60 as an easy-adhesion layer (B layer).

(Comparative Example 2-1)
A laminated biaxially stretched polyamide film was produced in the same manner as in Example 2-2, except that 100% by mass of polyamide 6 was melt-extruded as the base layer (A layer).

(Comparative Example 2-2)
Laminated biaxially oriented polyamide in the same manner as in Example 2 except that a mixture of polyamide 6 and polyamide 6/12 copolymer at a mass ratio of 50/50 was melt extruded as an easy adhesion layer (B layer). A film was produced.

Table 2 shows the water resistant laminate strength and other physical properties of the biaxially oriented polyamide films produced in Examples 2-1 to 2-4 and Comparative Examples 2-1 and 2-2.

As is clear from the results in Table 2, in the case of Examples 2-1 to 2-4 in which the easy-adhesion layer (B layer) contains 60% or more of the polyamide 6/12 copolymer, sufficient water resistant laminate strength is obtained.
On the other hand, Comparative Example 2-1 has poor pinhole resistance because it does not contain a polyamide elastomer, and Comparative Example 2-2 has a low content of polyamide 6/12 copolymer in the easy adhesion layer (B layer). , Sufficient water resistant laminate strength cannot be obtained.

As described above, the laminated stretched polyamide film of the present invention has been described based on a plurality of examples, but the present invention is not limited to the configurations described in the above examples, and the configurations described in each example are appropriately combined. etc., the configuration can be changed as appropriate without departing from the spirit thereof.

The laminated stretched polyamide film of the present invention is excellent in heat resistance, impact resistance, and pinhole resistance, and is also excellent in water-resistant adhesion (water-resistant laminate strength). Therefore, it can be suitably used for packaging materials such as liquid packaging.
The laminated stretched polyamide film of the present invention can be suitably used particularly for pickle bags, large-sized bags for commercial use, and the like.

Claims (6)

On at least one surface of a base layer (A layer) containing 97.5 to 80% by mass of polyamide 6 resin and 2.5 to 20% by mass of polyamide elastomer, the ratio of the copolymer component in the copolymer is 3 to An easy adhesion layer (layer B) containing 60 to 100% by mass of 35% by mass of polyamide 6 copolymer and 0 to 40% by mass of polyamide 6 is laminated, and the polyamide 6 copolymer is polyamide 6 / A laminated stretched polyamide film characterized by being a 66 copolymer or a polyamide 6/12 copolymer . 2. The laminated stretched polyamide film according to claim 1, wherein the A layer and the B layer are laminated in the order of A layer/B layer or B layer/A layer/B layer. 3. The laminated stretched polyamide film according to claim 1, wherein the layer A contains 0.5 to 30% by mass of a polyamide 6/66 copolymer. 3. The laminated stretched polyamide film according to claim 1, wherein the layer A contains 0.5 to 30% by mass of a polyamide 6/12 copolymer. The thickness of the laminated stretched polyamide film is 5 to 30 μm, the thickness of the layer A is 4.5 μm or more, and the thickness of the layer B is 0.5 μm or more. A laminated oriented polyamide film as described. 6. The laminated stretched polyamide film according to any one of claims 1 to 5 , which has a water resistant lamination strength of 2.0 N/15 mm or more.