Patent Application
20250187306
The present invention relates to a polyamide film, and relates to a polyamide film that has excellent cold formability and that can be suitably used for usage in which the film is molded after metal foil is laminated, in particular, for battery outer packages, medicine packaging, and the like.
A biaxially oriented polyamide film has excellent mechanical characteristics, thermal characteristics, and gas barrier properties, and is thus widely used for packaging materials of various foods and the like.
In recent years, laminate-type lithium ion battery outer packaging materials, press through packs, and the like have been obtained by cold-forming a multilayer body formed of a resin film and metal foil. For the multilayer body to be subjected to the cold-forming, a structure of, for example, a polyethylene terephthalate film/biaxially stretched nylon film/aluminum foil/polypropylene film, is used in general. (See, for example, Patent Document 1.)
Needs for a packaging form having foil of a metal such as aluminum have increased in order to prevent deterioration of contents also in medicine packaging, and formability of the metal foil according to the shape of the content is required to be enhanced.
A factor that affects formability in cold forming is, for example, flexibility of a resin film. In a case where a resin film has low flexibility, high load is applied to the film during elongation in the cold forming, so that pinholes or delamination may occur. Meanwhile, in a case where a resin film has excessively high flexibility, an effect of protecting a multilayer body including metal foil, as a base material, is reduced, and the obtained multilayer body has degraded physical properties. Therefore, it is important for the resin film to have flexibility which is not excessively high and not excessively low.
In order to solve the problems, for example. Patent Document 2 discloses a multilayer body in which at least a base layer, an adhesive layer, a metal layer, and a sealant layer are sequentially stacked, and indicates that good formability is obtained by setting to be a sum (A+B) of a value A of stress at 50% elongation/stress at 5% elongation in the MD direction, and a value B of stress at 50% elongation/stress at 5% elongation in the TD direction within a specific range in the base layer.
Meanwhile, in the above-described cold forming, a phenomenon (springback) that, after draw-forming, a part of the formed product is returned from a shape after the forming to a shape before the forming, may become a problem. Such springback may cause a problem that dimensional accuracy of the shape after the draw-forming is insufficient. Furthermore, since a portion around a to-be-formed portion is strongly drawn during a forming process, and a base layer around the formed portion may thus be returned to a shape before the forming when the forming process has been performed, warpage occurs and a yield may be reduced in the post-processing.
Even if an F5 value and an F50 value of the film are merely controlled as in Patent Document 2 indicated above for addressing these problems, although a forming depth is improved, the technique disclosed therein is insufficient for addressing reduction of dimensional accuracy caused by springback after the forming, and improving warp resistance after the forming.
Furthermore, in a biaxially oriented polyamide film produced by a biaxial stretching method, variation in physical properties in the film width direction is likely to occur. One of causes of the variation in physical properties in the width direction is considered to be a bowing phenomenon. The bowing phenomenon is considered to be a phenomenon in which, when a temperature becomes high in a heat-setting process, and shrinkage stress occurs in the longitudinal direction, the center portion of the film shrinks due to a low holding force while both end portions of the film are held by clips, and the main axis of the orientation is tilted in the width direction so as to bow.
Due to the bowing phenomenon, the main axis (angle indicating the largest value) of physical property values such as a heat shrinkage rate, a rate of dimensional change due to moisture absorption, and a refractive index varies in the film width direction. This increases a difference in physical property values such as the heat shrinkage rate and the rate of dimensional change due to moisture absorption in the diagonal direction. That is, in a case where cold forming is performed by using a multilayer body in which a biaxially oriented polyamide film obtained by the conventional method is used, the main axis direction of the orientation varies depending on a position in the width direction at which the film is taken, so that difference of formability occurs, and stable formability may not be obtained.
The present invention has been made in view of such problems of conventional art. An object of the present invention is to provide a polyamide film that has excellent cold formability regardless of a position in the width direction at which the film is taken, and further inhibits dimensional accuracy from being reduced due to springback after forming, and has excellent warp resistance.
The inventors of the present invention have found, as a result of thorough studies, that, in a case where a specific stretching condition range is selected, and mechanical characteristics of the film are controlled to be in a predetermined range, excellent cold formability can be obtained and springback and curling after forming can be inhibited, and have achieved the present invention.
That is, the present invention has the following configurations.
A biaxially oriented polyamide film comprising
stress attenuation rate (%)=100×(σ0−σ1)/σ0 Formula (1)
The biaxially oriented polyamide film according to Item 1, wherein the following (d) is further satisfied,
100 MPa≤Y(MD)≤150 MPa Formula (2)
110 MPa≤Y(TD)≤200 MPa Formula (3)
1.45≤Z(MD)≤2.2 Formula (4)
2.5≤Z(TD)≤3.5 Formula (5)
The polyamide film according to Item 1 or 2, wherein a strain at moisture absorption is 1.3% or less.
The biaxially oriented polyamide film according to any one of Items 1 to 3, wherein the biaxially oriented polyamide film is used for cold forming.
A multilayer body comprising:
The multilayer body according to Item 5, wherein the gas barrier layer includes metal foil.
A battery outer package material comprising the multilayer body according to Item 5 or 6.
By using the biaxially oriented polyamide film of the present invention as a base layer, metal foil is allowed to appropriately follow the shape of the mold during forming. Therefore, occurrence of pinholes, cracks, and the like can be inhibited and furthermore, springback and warp resistance after forming are excellent, so that dimensional accuracy in forming is excellent, and furthermore, contribution to enhancement of productivity can also be made.
The present invention will be described below in detail.
A biaxially oriented polyamide film of the present invention is formed of a polyamide resin composition preferably including 60 mass % or more of polyamide 6, more preferably including 80 mass % or more of polyamide 6, and further preferably including 90 mass % or more of polyamide 6. In a case where 60 mass % or more of polyamide 6 is included, excellent mechanical strength such as impact strength and excellent gas barrier properties can be obtained.
The polyamide 6 used in the present invention is produced by ring-opening polymerization of ε-caprolactam in general. The polyamide 6 obtained by ring-opening polymerization is dried and then melt-extruded by an extruder after lactam monomers are removed by using hot water in general.
The relative viscosity of the polyamide 6 is preferably 1.8 to 4.5 and more preferably 2.6 to 3.2. If the relative viscosity is less than 1.8, the film may have insufficient impact strength. If the relative viscosity is more than 4.5, a load on the extruder is increased, and it may be difficult to obtain a non-stretched film before stretching. The polyamide 6 used in the present invention may be polyamide 6 that is commercially available from UBE Corporation, BASF, or the like. Particularly, polyamide 6 which is commercially available as polyamide 6 for films, has the above-described relative viscosity, has a residual lactam monomer content of 1 mass % or less, has blocked or modified terminals, and is unlikely to generate lactam monomers during melting, is preferable.
As the polyamide 6, in addition to generally used polyamide 6 obtained by polymerization from monomers derived from fossil fuel, polyamide 6 that is chemically recycled from waste polyamide 6 products such as waste plastic products, waste tire rubber, fibers, and fishing nets can also be used. Examples of a method for obtaining the polyamide 6 chemically recycled from the waste polyamide 6 products include a method in which used polyamide products are collected and the collected products are thereafter depolymerized to obtain ε-caprolactam, and the ε-caprolactam is refined and polyamide 6 is obtained through polymerization.
In addition, polyamide 6 obtained by mechanically recycling waste materials discharged in the polyamide film producing process can be used in combination. The mechanically recycled polyamide 6 refers to, for example, a raw material obtained in a manner in which off-specification films that are generated during production of biaxially stretched polyamide films and cannot be shipped or waste materials generated as cut end materials (selvage trims) are collected and pelletized through melt-extrusion or compression molding.
The biaxially oriented polyamide film of the present invention may include a thermoplastic resin other than the polyamide 6 used as a main component in order to improve stretchability, pinhole resistance, ease of cutting, and the like. Furthermore, the biaxially oriented polyamide film may include a small amount of an additive such as an anti-blocking agent, a lubricating agent, an antistatic agent, a thermal stabilizer, and a light resisting agent.
Examples of the thermoplastic resin other than the polyamide 6 used in the present invention include homopolymers or copolymers of polyamide-based resins, polyester-based resins, polyolefin-based resins, acrylic-based resins, polycarbonate-based resins, polyvinyl-based resins, and urethane-based resins.
According to one mode of the present invention, the biaxially oriented polyamide film may include polyamide MXD6 and/or polyamide 61 in order to enhance stretchability when the film is formed. The content of these polyamides is preferably 20 mass % or less, more preferably 10 mass % or less, and further preferably 5 mass % or less with respect to a resin composition forming the biaxially oriented polyamide film.
According to one mode of the present invention, the biaxially oriented polyamide film may include a polyamide elastomer, a polyester elastomer, a polyolefin elastomer, or the like in order to enhance pinhole resistance.
According to one mode of the present invention, the biaxially oriented polyamide film may include inorganic particulates of silica, kaolin, zeolite, or the like, or crosslinked polymeric particulates of acryl, polystyrene, or the like as an anti-blocking agent or a lubricant. Silica particulates are suitably used from the viewpoint of transparency and slipperiness.
According to one mode of the present invention, the biaxially oriented polyamide film may include an organic lubricating agent having an effect of lowering surface energy, as a lubricating agent, to the extent that problems as to adhesiveness and wettability do not arise. Examples of the organic lubricating agent include ethylenebisstearamide (EBS). Using the combination of the above-described anti-blocking agent and lubricating agent is preferable, because excellent slipperiness and transparency can be imparted to the film simultaneously by using the combination.
A method for obtaining the biaxially oriented polyamide film of the present invention is not particularly limited and can be selected as appropriate, and may be, for example, a T-die method or an inflation method. A typical production process in which a T-die method is used will be described. The T-die method includes (1) melt-extruding a polyamide resin composition into a sheet-like shape and cooling the obtained sheet on a cooling roll to form an unstretched sheet, (2) a stretching step of stretching the formed unstretched sheet in an MD direction (longitudinal direction) and a TD direction (width direction) orthogonal to the MD direction, (3) a heat-setting step of heating and crystallizing the film having been subjected to the stretching step. (4) a thermal relaxation step (may also be referred to as relaxing step) of removing residual strain of the film having been subjected to the heat-setting step, and (5) a cooling step of cooling the film after the thermal relaxation.
The film of the present invention may have at least a monolayer structure formed of one layer or have a multilayer structure formed of two or more layers. The film may have two layers, three layers, four layers, or five layers.
As one mode for obtaining the biaxially oriented polyamide film of the present invention, a step of performing preliminary stretching of the unstretched sheet in the MD direction at a low ratio, and thereafter performing main stretching in the MD direction at a high ratio, is preferably included.
The above-described MD preliminary stretching is preferably performed with one stage or two stages. The total stretching ratio obtained by multiplying the stretching ratios in the respective MD preliminary stretchings is preferably 1.005 times or more and 1.15 times or less. If the stretching ratio is excessively low in the MD preliminary stretching, an effect of improving strain at moisture absorption as described below is not easily obtained. Meanwhile, in a case where the preliminary stretching ratio is 1.15 times or less, progress of oriented crystallization can be prevented, and breakage can be inhibited from being caused during the main stretching or TD stretching due to stretching stress becoming excessively high in the succeeding MD main stretching.
The temperature for the MD preliminary stretching is preferably [glass-transition temperature (the unit is ° C., hereinafter abbreviated as Tg) of the polyamide resin composition+20]° C. or higher and [low-temperature crystallization temperature (the unit is ° C., hereinafter abbreviated as Tc) of the polyamide resin composition+20]° C. or lower. Tg and Tc are values obtained by measurement in which the method described in Examples is used. By performing the MD preliminary stretching at a temperature of (Tg+20)° C. or higher, necking can be prevented, and unevenness in thickness can be reduced. By performing the stretching at a temperature of (Tc+20)° C. or lower, progress of thermal crystallization can be prevented, and breakage can be inhibited in the TD stretching process. The stretching temperature is more preferably (Tg+30)° C. or higher and (Tc+10)° C. or lower. For the MD preliminary stretching, a known longitudinal stretching method such as thermal roll stretching or infrared radiation stretching can be used.
The MD main stretching is preferably performed in two or more stages. The ratio of the first stage of the MD main stretching is preferably 1.1 times or more and 2.9 times or less. If the stretching ratio in the first stage of the main machine direction stretching is excessively low, the stretching effect is not obtained. Meanwhile, in a case where the stretching ratio in the first stage is 2.9 times or less, progress of oriented crystallization can be prevented.
In the MD main stretching, the stretching temperature at the first stage is preferably (Tg+20)° C. or higher and (Tc+20)° C. or lower. If the stretching temperature is lower than (Tg+20)° C., stretching stress becomes high, and breakage is likely to occur in the TD stretching. If the stretching temperature is higher than (Tc+20)° C., unevenness in thickness may be increased. The stretching temperature is more preferably (Tg+25)° C. or higher and (Tc+10)° C. or lower. In the first stage of the MD main stretching, a known MD stretching method such as thermal roll stretching or infrared radiation stretching can be used.
The ratios in the second and the succeeding stages of the MD main stretching are set such that the total stretching ratio obtained by multiplying the stretching ratios including the MD preliminary stretching ratios is preferably 2.8 times or more and 5.0 times or less, more preferably 3.0 times or more and 3.8 times or less, and further preferably 3.0 times or more and 3.6 times or less. If the total stretching ratio is less than 2.8 times, although variation in physical properties of the biaxially oriented film in the width direction is reduced, strength in the longitudinal direction may be reduced. If the total machine direction stretching ratio is excessively large, an effect of reducing variation in physical properties of the biaxially oriented film in the width direction may not be exhibited.
The stretching temperature at the second stage in the MD main stretching is preferably (Tg+20)° C. or higher and (Tc+20)° C. or lower and more preferably (Tg+25)° C. or higher and (Tc+10)° C. or lower. If the stretching temperature is lower than (Tg+20)° C., stretching stress becomes high, and breakage is likely to occur in the TD stretching. If the stretching temperature is higher than (Tc+20)° C., unevenness in thickness may be increased.
A thermal roll stretching method is preferably used at the second stage of the MD main stretching. As the thermal roll, a ceramic roll having a surface roughness Ra of 0.2 μm or less is preferably used. Using a roll having the Ra of more than 0.2 μm is not preferable, because stretching may be performed in a state where the film slides on the roll, and abrasion may disadvantageously occur on the film surface. The stretching start points on the roll may become non-uniform in the width direction, or the stretching start point may vary, so that the thickness may become uneven. At the second stage in the MD main stretching, regardless of the thickness profile, in the width direction, of the film having been subjected to the first stage of the MD main stretching, the film is preferably stretched on the roll in a state of being linearly in close contact therewith in the width direction, and heated and stretched uniformly in the width direction. In the description herein, Ra represents a center line average roughness and represents an average projecting and recessed height (unit=μm), and is a value defined by JIS B 0601.
In the stretching process, a relaxing step (hereinafter, also referred to as MD relaxation) in the MD direction is preferably performed before the TD direction stretching process following the MD direction stretching process. The lower limit of the MD relaxation rate is preferably 1%, more preferably 3%, and particularly preferably 5%. In a case where the MD relaxation rate is 1% or more, amorphous components in the film may be relaxed, and the stretching stress can be lowered in the succeeding TD direction stretching process, so that the orientation of the film can be inhibited from being excessively high, and springback and curling after forming can be inhibited. The upper limit of the MD relaxation rate is preferably 10%, more preferably 8%, and particularly preferably 6%. In a case where the MD relaxation rate is 10% or less, wrinkling due to shrinkage can be inhibited, and the quality of the film can be enhanced, and furthermore, mechanical strength can be inhibited from being reduced due to orientation relaxation. Examples of the MD relaxation method include, but are not particularly limited to, a method in which the relaxing process is performed by using difference in speed between rolls after heating is performed by a hot air heater.
The lower limit of the stretching temperature in the TD direction is preferably 90° C., more preferably 100° C., and particularly preferably 110° C. In a case where the stretching temperature in the TD direction is 90° C. or higher, the stretching stress can be lowered, and springback and curling after forming can thus be inhibited. The upper limit of the stretching temperature in the TD direction is preferably 140° C. more preferably 130° C., and particularly preferably 120° C. If the stretching temperature in the TD direction is higher than 140° C., a film forming property may be degraded, and, furthermore, orientation of the obtained film in the TD direction may be low, so that formability may be degraded.
The lower limit of the stretching ratio in the TD direction is preferably 2.5 times, more preferably 3.0 times, and particularly preferably 3.5 times. In a case where the stretching ratio in the TD direction is 2.5 times or more, the film has good mechanical strength and thickness variation properties, and furthermore, formability is enhanced. The upper limit of the stretching ratio in the TD direction is preferably 5.0 times, more preferably 4.5 times, and particularly preferably 4.0 times. In a case where the stretching ratio in the TD direction is 5.0 times or less, the orientation in the TD direction is inhibited from being high, and springback and curling after forming can be inhibited.
As the stretching pattern in the TD direction, not only a generally used linear stretching pattern in which the stretching ratio is linearly increased, but also multi-stage stretching can be preferably used. In the multi-stage stretching, two or more stages are performed in the stretching process as in the example illustrated in
The number of stages in the multi-stage stretching in the TD direction is preferably two or more and five or less. The multi-stage stretching is preferable since each of the stretching temperatures can be changed and the stretching stress can be changed, and the stretching stress during the TD direction stretching can be lowered. In a case where the number of stages in the stretching is two or more, stretching stress can be lowered, and, even when the stretching ratio is the same, orientation in the TD direction can be inhibited from being excessively high, and springback and curling after forming can be inhibited. In a case where the number of stages in the stretching is five or less, the equipment can be prevented from being excessively large. In the multi-stage stretching, a temperature pattern in which the temperature is reduced from the first stage of stretching to the final stage of stretching such that the temperature is made different by 2° C. or more per each stage of stretching, is preferable. In a case where the multi-stage stretching is performed, a zone having a fixed length can be provided following each stretching stage as appropriate. In a case where the zone having a fixed length is provided following each stretching stage, stretching stress can be further lowered in the succeeding stretching by relaxing, in the fixed length zone, internal stress generated during the stretching, and, even when the stretching ratio is the same, orientation in the TD direction can be inhibited from being excessively high, and springback and curling after forming can be inhibited.
In the heat-setting process, the lower limit of the heat-setting temperature is preferably 170° C., more preferably 180° C., and particularly preferably 190° C. At a heat-setting temperature of 170° C. or higher, the heat shrinkage rate can be reduced. The upper limit of the heat-setting temperature is preferably 230° C., more preferably 220° C., and particularly preferably 210° C. At a heat-setting temperature of 230° C. or lower, mechanical strength can be inhibited from being reduced due to the biaxially oriented polyamide film becoming brittle.
In the thermal relaxation process, the lower limit of the relaxation rate in the TD direction is preferably 0.5%, more preferably 1.0%, and particularly preferably 2.0%. In a case where the relaxation rate is 0.5% or more, the heat shrinkage rate in the TD direction can be maintained to be low. The upper limit of the relaxation rate in the TD direction is preferably 10%, more preferably 8%, and particularly preferably 6%. In a case where the relaxation rate is 10% or less, looseness and the like can be prevented and planarity can be enhanced.
The biaxially oriented polyamide film of the present invention can also be subjected to corona treatment, coating treatment, flame treatment, or the like in order to further enhance adhesiveness and wettability. The above-described treatment can also be performed while the biaxially oriented polyamide film is being produced. The treatment may be performed by winding off a mill roll or slit roll.
The lower limit of the thickness of the biaxially oriented polyamide film of the present invention is preferably 5 μm and more preferably 10 μm. In a case where the thickness thereof is 5 μm or more, good mechanical characteristics and formability can be obtained. The upper limit of the thickness of the biaxially oriented polyamide film of the present invention is preferably 100 μm, more preferably 70 μm, and particularly preferably 40 μm.
The lower limit of piercing strength of the biaxially oriented polyamide film of the present invention is preferably 0.5 N/μm and more preferably 0.6 N/μm. In a case where the piercing strength is 0.5 N/μm or more, good formability can be obtained. The upper limit of the piercing strength of the biaxially oriented polyamide film of the present invention is, but is not particularly limited to, preferably 1.0 N/μm or less. If the piercing strength is more than 1.0 N/μm, an effect of enhancing formability may be saturated. In the present invention, the piercing strength (unit is N/μm) is a value obtained by dividing strength (unit is N) obtained when a needle having a tip radius of 0.5 mm pierces the film at a piercing speed of 50 mm/minute and the needle penetrates through the film by the thickness (unit is μm) of the film.
The lower limit of heat shrinkage rate of the biaxially oriented polyamide film of the present invention is preferably 0.5%, more preferably 0.8%, and particularly preferably 1.0% in the MD direction and the TD direction. The upper limit of heat shrinkage rate of the biaxially oriented polyamide film of the present invention is preferably 3.0%, more preferably 2.5%, and particularly preferably 2.0% in the MD direction and the TD direction. In a case where the heat shrinkage rate is 3.0% or less, dimensional change can be inhibited when heating is performed in a secondary processing step, and wrinkling can be inhibited.
Next, springback during forming will be described.
In a case where molding is performed for battery outer packages, medicine packaging, and the like, the film is pressed into a mold having a predetermined shape, the film is thereafter held for a certain time period in the pressed state, and the mold is thereafter taken up to produce a molded body. If the mold is taken up in a state where the internal stress in the film is not sufficiently relaxed in the holding time period, a force for returning the film to an original shape acts, and springback is increased, so that dimensional accuracy of the molded body may be reduced. The inventors of the present invention have found that the springback can be reduced in a case where the stress attenuation rate of the film having been held for two seconds is within a specific range in a tensile stress relaxation test of the obtained biaxially oriented polyamide film.
In the biaxially oriented polyamide film of the present invention, the stress attenuation rate indicated by the following Formula (1) is preferably 12% or more and more preferably 14% or more in each of the MD direction and the TD direction in the tensile stress relaxation test at 25° C.
stress attenuation rate (%) after the film is held for two seconds=100×(σ0−σ1)/σ0 Formula (1)
In the formula (1), σ0 represents a value of a tensile stress of the film, which is obtained immediately after a 50% tensile strain is applied to the film by applying a tensile force at a tensile rate of 200 mm/min, and σ1 represents a value of a tensile stress obtained when the 50% tensile strain is held for two seconds from σ0.
In the biaxially oriented polyamide film of the present invention, when Y(MD) represents a stress (F30 value) at 30% elongation at 25° C. in the MD direction of the film, and Y(TD) represents a stress (F30 value) at 30% elongation at 25° C. in the TD direction, the following Formulas (2) and (3) are preferably satisfied.
100 MPa≤Y(MD)≤150 MPa Formula (2)
110 MPa≤Y(TD)≤200 MPa Formula (3)
In a case where the value of Y(MD) is 100 MPa or more, excellent formability can be obtained. Meanwhile, in a case where the value of Y(MD) is 150 MPa or less, stress of the film after the molding can be inhibited from being excessively high, springback and warp resistance after the molding can be reduced, and good formability can be obtained. Similarly, in a case where the value of Y(TD) is 110 MPa or more, excellent formability can be obtained. In a case where the value of Y(TD) is 200 MPa or less, stress of the film after the molding can be inhibited from being excessively high, springback and warp resistance after the molding can be reduced, and good formability can be obtained.
In the biaxially oriented polyamide film of the present invention, when X(MD) represents a stress (F3 value) at 3% elongation at 25° C. in the MD direction of the film, X(TD) represents a stress (F3 value) at 3% elongation at 25° C. in the TD direction, Z(MD) represents a value of Y(MD)/X(MD), and Z(TD) represents a value of Y(TD)/X(TD), the following Formulas (4) and (5) are preferably satisfied.
1.45≤Z(MD)≤2.2 Formula (4)
2.5≤Z(TD)≤3.5 Formula (5)
In a case where the value of Z(MD) is 1.4 or more, excellent formability can be obtained. Meanwhile, in a case where the value of Z(MD) is 2.2 or less, stress of the film after the molding can be inhibited from being excessively high, springback and warp resistance after the molding can be reduced, and good formability can be obtained. Similarly, in a case where the value of Z(TD) is 12.5 or more, excellent formability can be obtained. In a case where the value of Z(TD) is 3.5 or less, stress of the film after the molding can be inhibited from being excessively high, springback and warp resistance after the molding can be reduced, and good formability can be obtained.
In the biaxially oriented polyamide film of the present invention, a strain at moisture absorption as determined by the measurement method indicated below in Examples is preferably 1.3% or less and more preferably 1.1% or less. If the strain at moisture absorption is more than 1.3%, the orientation direction of the main axis varies depending on the position at which the film is taken, so that stable formability may not be obtained.
The biaxially oriented polyamide film of the present invention may have a printed layer stacked therein. As a printing ink for forming the printed layer, an aqueous or solvent-based resin-containing printing ink can be preferably used. Examples of the resin used for the printing ink include acrylic resins, urethane-based resins, polyester-based resins, vinyl-chloride-based resins, vinyl acetate copolymer resins, and mixtures thereof. The printing ink may contain known additives such as an antistatic agent, a light-blocking agent, an ultraviolet absorber, a plasticizer, a lubricant, a filler, a colorant, a stabilizer, a lubricating agent, a defoamer, a crosslinking agent, an anti-blocking agent, and an antioxidant.
A printing method for forming the printed layer is not particularly limited, and a known printing method such as an offset printing method, a gravure printing method, and a screen printing method can be used. For drying the solvent after the printing, a known drying method such as a hot air-drying method, a thermal roll drying method, and an infrared drying method can be used.
The present invention further provides a multilayer body in which a gas barrier layer such as an inorganic thin film layer or metal foil is disposed at the biaxially oriented polyamide film.
The inorganic thin film layer is a thin film formed of a metal or an inorganic oxide. The material forming the inorganic thin film layer is not particularly limited as long as the thin film can be formed of the material. Preferable examples of the material include aluminum, and inorganic oxides such as silicon oxide (silica), aluminum oxide (alumina), and mixtures of silicon oxide and aluminum oxide from the viewpoint of gas barrier properties. Particularly, a composite oxide of silicon oxide and aluminum oxide is preferable from the viewpoint of achieving both flexibility and denseness of the thin film layer.
In the composite oxide, as a mixing ratio between silicon oxide and aluminum oxide, a ratio of Al preferably ranges from 20 to 70% in terms of mass ratio of metal contents. In a case where the ratio of Al is 70% or less, the inorganic thin film layer can be made flexible, and gas barrier properties can be inhibited from being degraded due to the thin film being broken in a secondary process such as printing and lamination. In the description herein, the silicon oxide represents various silicon oxides such as SiO and SiO2, or mixtures thereof, and the aluminum oxide represents various aluminum oxides such as AlO and AL2O3, or mixtures thereof.
The film thickness of the inorganic thin film layer is 1 to 100 nm in general, and preferably 5 to 50 nm. In a case where the film thickness of the inorganic thin film layer is 1 nm or less, more satisfactory gas barrier properties are likely to be obtained. Meanwhile, the thickness of 100 nm or less is advantageous from the viewpoint of bending resistance and production cost.
A method for forming the inorganic thin film layer is not particularly limited. For example, a known vapor deposition method, the examples of which include physical vapor deposition methods (PVD methods) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, and chemical vapor deposition methods (CVD methods), can be adopted as appropriate. A typical method for forming the inorganic thin film layer will be described below by using a silicon oxide/aluminum oxide-based thin film as an example. For example, in a case where a vacuum vapor deposition method is adopted, a mixture of SiO2 and Al2O3, a mixture of SiO2 and Al, or the like is preferably used as a vapor deposition raw material. Particles are used as the vapor deposition raw material in general. In this case, the size of each particle is desirably a size that does not change the pressure during vapor deposition, and the particle size is preferably 1 to 5 mm. For heating, systems such as resistive heating, high frequency induction heating, electron beam heating, and laser heating can be adopted. It is also possible to adopt reactive vapor deposition in which oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor, or the like is introduced as a reaction gas or a means such as ozone addition or ion assist is used. Furthermore, a film formation condition such as biasing a body to be vapor-deposited (multilayer film to be vapor-deposited) and heating or cooling the body to be vapor-deposited can also be discretionarily changed. Similarly, the vapor deposition materials, reaction gases, biasing of the body to be vapor-deposited, heating/cooling, and the like can be changed also when a sputtering method or a CVD method is adopted. Furthermore, a printed layer may be stacked on the inorganic thin film layer.
In a case where the inorganic thin film layer is provided at the biaxially oriented polyamide film of the present invention, a protective layer is preferably disposed on the inorganic thin film layer. The gas barrier layer formed of metal oxide is not a completely dense film, and minute defect portions are dotted. By applying a specific resin composition for the protective layer as described below onto the metal oxide layer to form the protective layer, resin in the protective phase solvent resin composition permeates into the defect portions of the metal oxide layer, so that an effect of stabilizing the gas barrier properties is obtained. In addition, by using a material having gas barrier properties also for the protective layer itself, the gas barrier performance of the multilayer film may also be significantly enhanced.
The protective layer is, for example, a layer in which an epoxy-based, an isocyanate-based, or a melamine-based curing agent, or the like is added to a urethane-based, a polyester-based, an acryl-based, a titanium-based, an isocyanate-based, an imine-based, or a polybutadiene-based resin, or the like. Examples of a solvent used for forming the protective layer include aromatic solvents such as benzene and toluene; alcohol-based solvents such as methanol and ethanol; ketone-based solvents such as acetone and methyl ethyl ketone; ester-based solvents such as ethyl acetate and butyl acetate; and polyhydric alcohol derivatives such as ethylene glycol monomethyl ether.
As the metal foil used for the gas barrier layer, various metal foils such as aluminum foil and stainless steel foil can be used, and aluminum foil is preferable from the viewpoint of moisture resistance, processability such as extendability, and cost. As aluminum foil, standard soft aluminum foils can be used. Among them, aluminum foil containing iron is preferable from the viewpoint of excellent pinhole resistance and excellent extendability during molding. A content of iron in aluminum foil (100 mass %) containing iron is preferably 0.1 to 9.0 mass % and more preferably 0.5 to 2.0 mass %. In a case where the content of the iron is the lower limit value or more, pinhole resistance and extendability are excellent. In a case where the content of the iron is 9.0 mass % or less, flexibility is excellent. The thickness of the metal foil is preferably 9 to 200 μm and more preferably 15 to 100 μm from the viewpoint of barrier properties, pinhole resistance, and processability.
A layer formed of another material may be stacked at the multilayer body of the present invention. For example, a method in which the biaxially oriented polyamide film and a biaxially oriented polyester film are adhered after film formation, or a method in which these films are adhered during film formation, can be adopted.
The multilayer body of the present invention can further have a heat-sealable resin layer (also referred to as sealant layer) called a sealant, in addition to the biaxially oriented polyamide film and the gas barrier layer, and can be used as a packaging material for cold forming. According to another mode of the present invention, the multilayer body can further have a heat-sealable resin layer (also referred to as sealant layer) called a sealant, in addition to a biaxially oriented polyester film, the biaxially oriented polyamide film, and the gas barrier layer, and can be used as a packaging material for cold forming. The sealant layer is formed by an extrusion lamination method or dry lamination method in general.
Examples of the sealant layer include a resin film formed of a polyolefin-based resin, or an acid-modified polyolefin-based resin obtained by graft-modifying polyolefin-based resin with acid such as maleic anhydride. Examples of the polyolefin-based resin include low-density, medium-density, and high-density polyethylenes; ethylene-α olefin copolymers; homo-, block- and random-polypropylenes; and propylene-α olefin copolymers. One of these polyolefin-based resins may be used alone, or two or more of them may be used in combination.
The sealant layer may be a monolayer film or a multilayer film, and may be selected according to the required function. For example, a multilayer film that includes therein resin such as an ethylene-cyclic olefin copolymer or polymethylpentene can be used in order to impart moisture resistance. In the sealant layer, various additives such as a flame retardant, a slipping agent, an anti-blocking agent, an antioxidant, a light stabilizer, and a tackifier may be blended. The thickness of the sealant layer is preferably 10 to 100 μm and more preferably 20 to 60 μm.
The multilayer body of the present invention can also have a structure in which the adhesive layer, the printed layer, or the like is disposed between the biaxially oriented polyamide film and a biaxially oriented polyester film, between the biaxially oriented polyamide film and the gas barrier layer, between a biaxially oriented polyester film and the gas barrier layer, and/or between the gas barrier layer and the sealant layer.
The present invention provides a battery outer package material that includes the multilayer body having the biaxially oriented polyamide film, the gas barrier layer, and the sealant layer. According to another mode, the present invention provides a battery outer package material that includes the multilayer body having a biaxially oriented polyester film, the biaxially oriented polyamide film, the gas barrier layer, and the sealant layer. Particularly, the present invention is suitably used for a battery outer package material for a laminate-type lithium ion battery. According to still another mode, the present invention provides a material for medicine packaging.
The film and the multilayer body were evaluated by the following measurement methods. Unless otherwise specified, the measurement was performed in a measurement room in an environment of 23° C. and a relative humidity of 65%.
The thickness was measured by using a dial gauge in accordance with the A method of JIS K7130-1999.
The heat shrinkage rate was measured by a dimensional change testing method based on JIS-C-2318 except that the test temperature was 160° C. and the heating time was ten minutes. A sample was cut out in each of the MD direction and the TD direction, and the measurement was performed.
The piercing strength was measured in accordance with “2. Testing methods for strength, etc.” in “Standards for Food, Additives, etc. Chapter III: Apparatus and Containers and Packaging” (Notification No. 20 of the Ministry of Health and Welfare, 1982) in the Food Sanitation Act. A needle having a tip radius of 0.5 mm was caused to pierce the film at a piercing speed of 50 mm/minute, and a value obtained by dividing the strength (N) obtained when the needle penetrated through the film by the thickness (μm) of the film was set as the piercing strength. The measurement was performed at a normal temperature (23° C.). The unit was N/μm.
A circle having a diameter of 200 mm was drawn around a position distant from the end portion of the biaxially oriented polyamide film mill roll by 300 mm. With the MD direction being defined as 0°, straight lines passing through the center of the circle were drawn in the 45° direction and the 135° direction. Subsequently, the sample was left as it was in an atmosphere of 30° C. and 80% RH for two or more hours. Thereafter, the diameter in each direction was measured, and was set as a length at high humidity. Thereafter, the sample was left as it was in a room at 20° C. and 40% RH for two or more hours, and the length of the straight line drawn in each diameter direction was thereafter measured again, and was set as a length at low humidity, and elongation at moisture absorption was calculated according to the following Formula (6). Thereafter, an absolute value (%) of a difference between heat shrinkage rates in the 450 direction and the 135° direction was calculated as the strain at moisture absorption.
elongation (%) at moisture absorption=[(length at high humidity−length at low humidity)/length at low humidity]×100 Formula (6)
A test sample was cut out in the film MD direction so as to have a width of 15 mm and a length of 100 mm in accordance with JIS K 7127. A tensile test for the test sample was performed by using a tensile tester (AUTOGRAPH AG-I manufactured by SHIMADZU CORPORATION) under conditions that a gauge length was 50 mm and a tensile rate was 200 mm/min. A stress value (F3) at 3% deformation of the test sample and a stress value (F30 value) at 30% deformation of the test sample were calculated according to the obtained stress-strain curve.
A test sample was cut out in the film MD direction so as to have a width of 15 mm and a length of 100 mm. A 50% tensile strain was applied by using a tensile tester (AUTOGRAPH AG-I manufactured by SHIMADZU CORPORATION) under conditions that a gauge length was 50 mm and a tensile rate was 200 mm/min, and the tensile strain was held from a time when the 50% tensile strain was applied to elapse of 100 seconds, and the change in the stress during the period was recorded.
The stress values from a time immediately after the 50% strain was applied to elapse of two seconds in a state where the strain was held were read from the obtained holding time-stress graph, and the stress attenuation rate after the strain was held for two seconds was obtained according to the following Formula (1).
stress attenuation rate (%) after the strain was held for two seconds=100×(σ0−σ1)/σ0 Formula (1)
In the formula, σ0 represents a tensile stress of the film, which was obtained immediately after the 50% tensile strain was applied to the film by applying a tensile force at the tensile rate of 200 mm/min, and σ1 represents a stress value obtained when the 50% tensile strain was held for two seconds from σ0.
A biaxially oriented polyester film (E5102 manufactured by TOYOBO Co., Ltd., the thickness was 12 μm), the biaxially oriented polyamide film, aluminum foil (8079 material, the thickness was 40 μm), and an unstretched polypropylene film (P1146 manufactured by TOYOBO Co., Ltd., the thickness was 70 μm) as a sealant layer were dry-laminated by using a urethane-based adhesive (dry laminate adhesive manufactured by Toyo-Morton, Ltd., a blending ratio among TM-509, CAT10L, and ethyl acetate was 33.6:4.0:62.4 (mass ratio)), and a multilayer body in which the biaxially oriented polyester film//the biaxially oriented polyamide film//the aluminum foil//the sealant layer were stacked in this order, was produced. The obtained multilayer body was set at a die set mold (90 mm×50 mm projection shape), and draw-forming was performed by applying pressure to the multilayer body at 23° C. with use of a pressing machine. The draw depth at the forming was increased in units of 0.2 mm, and the maximum depth at which breakage of the multilayer body was not caused was set as the draw depth. The evaluation was made according to the following criteria.
The above-described multilayer body was set at a die set mold (90 mm×50 mm projection shape), and draw-forming was performed by applying pressure to the multilayer body at 23° C. with use of a pressing machine. In the draw-forming, the rate at which the multilayer body was pressed into the mold was 200 mm/min, and the holding time after the pressing was two seconds. The depth of the container was measured after the mold was removed, and the retention rate (ratio between the depth of the container and the forming depth) was calculated. The evaluation was made according to the following criteria.
A sample which was able to be formed without being broken in the cold formability evaluation was placed on a level table such that the projection of the sample was on the upper side. The average value of heights by which four corners of the formed test piece were raised from the table as an originating point was set as the warp height average value, and the evaluation was made according to the following criteria.
The polyamide resins used in examples and comparative examples were as follows.
A polyamide 6 resin having an RV=2.9 and a melting point (Tm) of 220° C. was used.
A polyamide MDX6 resin having an RV=2.2 and a melting point (Tm) of 238° C. was used.
93.5 mass % of the above-described polyamide 6, 5 mass % of porous silica particulates (weight average particle diameter=3.0 μm, pore volume=1.8 ml/g), and 1.5 mass % of ethylene bis stearamide (manufactured by Kyoeisha Chemical Co., Ltd., LIGHT AMIDE WE-183) were blended, melt-knead-extruded by a twin-screw extruder, and cut into a pellet-like form to obtain a master batch.
The relative viscosity, the glass-transition temperature, the cold crystallization temperature, and the melting point of the resin were measured as follows.
For a polyamide solution obtained by dissolving 0.25 g of the above-described raw material polyamide with 96% sulfuric acid in a 25 ml measuring flask such that the concentration was 1.0 g/dl, the relative viscosity was measured at 20° C.
The melting point Tm was measured in the process of increasing the temperature of a pan containing 10 mg of an unstretched polyamide film from 30° C. to 280° C. at a temperature increase rate of 20° C./minute in a nitrogen atmosphere, by using a DSC-60 type differential scanning calorimeter manufactured by SHIMADZU CORPORATION, in accordance with JIS K7121. When the temperature reached 280° C., the pan containing the sample was immersed in liquid nitrogen and quenched, and the temperature of the pan was thereafter increased from 0° C. to 280° C. at a temperature increase rate of 10° C./minute, and the glass-transition temperature Tg and the cold crystallization temperature Tc were measured in the temperature increase process.
The raw materials were blended so as to contain 85 mass % of the polyamide 6, 3 mass % of the polyamide MXD6, and 12 mass % of the master batch of the silica particulates and the ethylenebisamide. The blended raw materials were extruded as a melted film by an extruder through a T-die at a temperature of 260° C. after a water content was adjusted to 0.1 mass %, and the melted film was electrostatically brought into close contact onto a metal roll having been cooled to 30° C. by applying a DC high voltage, and cooled and solidified, to obtain an unstretched film having a thickness of 200 μm. The unstretched film had a Tg of 41° C. and a Tc of 69° C.
By using a roll stretching machine, the unstretched film was stretched 1.03 times at a stretching temperature of 80° C. in the first stage of the MD preliminary stretching, and subsequently stretched 1.03 times at a stretching temperature of 80° C. in the second stage of the MD preliminary stretching. Subsequently, the film was stretched 2.1 times at 85° C. in the first stage of the MD main stretching, and further stretched 1.53 times at a stretching temperature of 70° C. in the second stage of the MD main stretching. The MD stretched film was sequentially guided to a tenter, and stretched 4.0 times at 130° C. in the TD direction, and thereafter heat-set at 210° C., and was further subjected to 5.0% relaxation at 210° C. in the TD direction. Subsequently, the film was cooled at 100° C., and one surface of the film was subjected to corona treatment, and thereafter, tenter-clip-held portions at both ends were each trimmed over a width of 150 mm, to obtain a biaxially oriented polyamide film mill roll having a thickness of 15 μm and a width of 6000 mm. Table 1 indicates the evaluation results of the obtained film.
As indicated in Table 1, polyamide films were each obtained in the same manner as in Example 1 except that the temperature and the ratio for the MD preliminary stretching and the ratio for MD main stretching were changed.
The raw materials were blended so as to contain 85 mass % of the polyamide 6, 3 mass % of the polyamide MXD6, and 12 mass % of the master batch of the silica particulates and the ethylenebisamide. The blended raw materials were extruded as a melted film by an extruder through a T-die at a temperature of 260° C. after a water content was adjusted to 0.1 mass %, and the melted film was electrostatically brought into close contact onto a metal roll having been cooled to 30° C. by applying a DC high voltage, and cooled and solidified, to obtain an unstretched film having a thickness of 200 μm. The unstretched film had a Tg of 41° C. and a Tc of 69° C.
By using a roll stretching machine, the unstretched film was stretched 1.07 times at a stretching temperature of 85° C. in the MD preliminary stretching, subsequently stretched 2.0 times at 85° C. in the first stage of the MD main stretching, and further stretched 2.0 times at a stretching temperature of 70° C. in the second stage of the MD main stretching. Immediately after the film was subjected to the MD stretching, the film was caused to pass through a heating oven having been set to 85° C. by a hot air heater, and was subjected to 5% relaxation in the MD direction by using difference in speed between a roll at an inlet of the heating oven and a roll at an outlet thereof. The MD stretched film was sequentially guided to a tenter, and stretched 4.0 times at 130° C. in the TD direction, and thereafter heat-set at 210° C., and was further subjected to 5.0% relaxation at 210° C. in the TD direction. Subsequently, the film was cooled at 100° C., and one surface of the film was subjected to corona treatment, and thereafter, tenter-clip-held portions at both ends were each trimmed over a width of 150 mm, to obtain a biaxially oriented polyamide film mill roll having a thickness of 15 μm and a width of 6000 mm. Table 1 indicates the evaluation results of the obtained film.
The raw materials were blended so as to contain 85 mass % of the polyamide 6, 3 mass % of the polyamide MXD6, and 12 mass % of the master batch of the silica particulates and the ethylenebisamide. The blended raw materials were extruded as a melted film by an extruder through a T-die at a temperature of 260° C. after a water content was adjusted to 0.1 mass %, and the melted film was electrostatically brought into close contact onto a metal roll having been cooled to 30° C. by applying a DC high voltage, and cooled and solidified, to obtain an unstretched film having a thickness of 200 μm. The unstretched film had a Tg of 41° C. and a Tc of 69° C.
By using a roll stretching machine, the unstretched film was stretched 1.03 times at a stretching temperature of 80° C. in the first stage of the MD preliminary stretching, and subsequently stretched 1.03 times at a stretching temperature of 80° C. in the second stage of the MD preliminary stretching. Subsequently, the film was stretched 2.1 times at 85° C. in the first stage of the MD main stretching, and further stretched 1.53 times at a temperature of 70° C. in the second stage of the MD main stretching. The MD stretched film was sequentially guided to a tenter. The stretching method at the tenter was changed to three-stage stretching, and a 1 m fixed length region was provided between the first stage and the second stage, and between the second stage and the third stage, and the film was stretched in the TD direction. Thereafter, the film was heat-set at 210° C., and was further subjected to 5.0% relaxation at 210° C. in the TD direction. Subsequently, the film was cooled at 100° C., and one surface of the film was subjected to corona treatment, and thereafter, the tenter-clip-held portions at both ends were each trimmed over a width of 150 mm, to obtain a biaxially oriented polyamide film mill roll having a thickness of 15 μm and a width of 6000 mm. Table 1 indicates the evaluation results of the obtained film.
As indicated in Table 2, biaxially oriented polyamide films were each obtained in the same manner as in Example 1 except that the MD preliminary stretching was not performed, the MD main stretching was performed by two-stage stretching at the temperatures and the ratios indicated in Table 2.
As indicated in Table 2, biaxially oriented polyamide films were each obtained in the same manner as in Example 1 except that the MD preliminary stretching was not performed, the MD main stretching was performed by two-stage stretching at the temperatures and the ratios indicated in Table 2, and the beat-setting temperatures and the relaxation rates after the TD stretching were changed to the temperatures indicated in Table 2.
As indicated in Table 2, a biaxially oriented polyamide film was obtained in the same manner as in Example 1 except that the MD preliminary stretching was not performed, the MD main stretching was performed by one-stage stretching at the temperature and the ratio indicated in Table 2.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2022-041876 | Mar 2022 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2023/004183 | 2/8/2023 | WO |
