JP6922070B2 - Laminated film, packaging material, packaging body and manufacturing method of laminated film - Google Patents

Description

The present invention relates to a laminated film, a packaging material, a package, and a method for producing a laminated film.

As a laminated film for packaging, a laminated film in which a heat-sealing layer made of low-density polyethylene or the like is bonded to a base film is known.
Examples of the technique related to such a laminated film include those described in Patent Document 1 (Japanese Unexamined Patent Publication No. 2017-202584).

Patent Document 1 describes a first layer of a pharmaceutical packaging film composed of a laminate of at least three thermoplastic resin forming layers, which is the innermost layer composed of an antioxidant-free thermoplastic resin forming layer and in contact with a medicine. A second layer composed of a thermoplastic resin-forming layer containing a polymer-type antistatic agent containing C% by weight (however, 10 <C <30) in a single layer of the polymer-type antistatic agent, and a thermoplastic resin-forming layer. The third layer of the outermost layer or the laminate from the third layer to the outermost layer is characterized in that the elution alkaline component in water is equivalent to 0.01 mmol at the maximum per 5 g of a total of 5 g of ^{2 pieces of 1 cm.} A film for pharmaceutical packaging is described.

JP-A-2017-202584

The technical standards required for various characteristics of laminated films for packaging are becoming higher and higher. The laminated film described in Patent Document 1 does not exhibit sufficient antistatic properties unless a polymer-type antistatic agent in an amount exceeding 10% by mass is contained in a single layer. Since the polymer type antistatic agent is generally expensive, if the content of the polymer type antistatic agent exceeds 10% by mass, it may not be practical from the viewpoint of price. Further, when the content of the polymer-type antistatic agent is increased, the transparency of the obtained laminated film is lowered, and the visibility of the contents may be deteriorated. Therefore, there is a demand for a laminated film that exhibits sufficient antistatic properties even if the content of the polymer-type antistatic agent in the single layer is small.

The present invention has been made in view of the above circumstances, and provides a laminated film having excellent antistatic properties.

The present inventors have made extensive studies to achieve the above problems. As a result, by forming an antistatic layer containing a thermoplastic resin and a polymer-type antistatic agent on the base material layer by using an extrusion coating method, the polymer-type antistatic agent is dispersed in the antistatic layer. It has been found that the properties are improved, and as a result, a laminated film having excellent antistatic properties can be obtained even when the content of the polymer-type antistatic agent in the single layer is low, and the present invention has been made.

That is, according to the present invention, the following methods for producing a laminated film, a packaging material, a package, and a laminated film are provided.

[1]
It was formed of a resin composition (B3) containing at least a base material layer (A), a thermoplastic resin (B1), and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
A laminated film in which the antistatic layer (B) is an extrusion coating processed layer formed by extrusion coating the resin composition (B3) on the base material layer (A).
[2]
It was formed of a resin composition (B3) containing at least a base material layer (A), a thermoplastic resin (B1), and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
The antistatic layer (B) is an extrusion coating processed layer.
A laminated film having an attenuation time of 1.0 second or less, which is measured by the following method.
(Method)
FEDERAL TEST METHOD 101C METHOD 4046 (US federal government test standard), using an electrostatic voltage attenuation characteristic measuring device, under the conditions of applied voltage 5000V, 23 ° C, 50% RH, the above base material layer (A) A voltage is applied to the surface of the band until the band voltage reaches 5000 V, and then the time for the band voltage to decay from 5000 V to 500 V is measured, and this time is defined as the decay time.
[3 ]
In the laminated film according to above SL [1] or [2],
Lamination in which the melt flow rate (MFR) of the thermoplastic resin (B1) is 0.1 g / 10 minutes or more and 20 g / 10 minutes or less as measured under the conditions of 190 ° C. and 2160 g load according to JIS K7210: 1999. Film .
[4 ]
In the laminated film according to any one of the above [1] to [ 3],
A laminated film having a thickness of the antistatic layer (B) of 5 μm or more .
[5 ]
In the laminated film according to any one of the above [ 1 ] to [4],
Laminated film containing at least one metal ion constituting the ethylene-based ionomer over is selected from potassium ion, lithium ion and sodium ion.
[ 6 ]
In the laminated film according to any one of the above [1] to [ 5],
A laminated film in which the base material layer (A) contains at least one selected from the group consisting of a polyester film, a nylon film and a polyolefin film.
[ 7 ]
In the laminated film according to any one of the above [1] to [ 6],
A laminated film in which the heat-sealing layer (C) contains polyolefin.
[ 8 ]
A packaging material including at least a layer composed of the laminated film according to any one of the above [1] to [ 7].
[ 9 ]
A packaging body comprising the packaging material according to the above [ 8 ] and an article packaged by the packaging material.
[ 10 ]
It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A method for producing a laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
A laminated film comprising an extrusion step of forming the antistatic layer (B) on the base material layer (A) by extrusion-coating the resin composition (B3) on the base material layer (A). Production method.

According to the present invention, it is possible to provide a laminated film having excellent antistatic properties.

The above-mentioned objectives and other objectives, features and advantages will be further clarified by the preferred embodiments described below and the accompanying drawings below.

It is sectional drawing which shows typically an example of the structure of the laminated film of embodiment which concerns on this invention.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Unless otherwise specified, "X to Y" in the numerical range represents X or more and Y or less.

1. 1. Laminated film and manufacturing method of laminated film FIG. 1 is a cross-sectional view schematically showing an example of the structure of the laminated film 10 according to the embodiment of the present invention.
The laminated film 10 according to the present embodiment is a resin containing at least a base material layer (A), a thermoplastic resin (B1), and a polymer antistatic agent (B2) (however, excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) formed by the composition (B3) and a heat-sealing layer (C) in this order, and is a polymer type in the antistatic layer (B). The content of the antistatic agent (B2) is 1% by mass or more and 10% by mass or less when the entire antistatic layer (B) is 100% by mass, and the antistatic layer (B) is the base material. It is an extruded coating processed layer formed by extruding the resin composition (B3) on the layer (A).
Further, in the method for producing the laminated film 10 according to the present embodiment, at least the base material layer (A), the thermoplastic resin (B1) and the polymer antistatic agent (B2) (however, the thermoplastic resin (B1)) are used. A method for producing a laminated film including an antistatic layer (B) formed of a resin composition (B3) containing (excluding) and a heat-sealing layer (C) in this order, wherein the antistatic layer is provided. The content of the polymer-type antistatic agent (B2) in (B) is 1% by mass or more and 10% by mass or less, assuming that the entire antistatic layer (B) is 100% by mass, and the base material layer. It includes an extrusion step of forming an antistatic layer (B) on a base material layer (A) by extrusion-coating the resin composition (B3) on (A). That is, the antistatic layer (B) of the laminated film 10 according to the present embodiment is an extrusion coating processed layer formed by the extrusion coating method.

As described above, the laminated film described in Patent Document 1 does not exhibit sufficient antistatic properties unless a polymer-type antistatic agent in an amount exceeding 10% by mass is contained in the single layer. Since the polymer type antistatic agent is generally expensive, if the content of the polymer type antistatic agent exceeds 10% by mass, it may not be practical from the viewpoint of price. Further, when the content of the polymer-type antistatic agent is increased, the transparency of the obtained laminated film is lowered, and the visibility of the contents may be deteriorated. Therefore, there is a demand for a laminated film that exhibits sufficient antistatic properties even if the content of the polymer-type antistatic agent in the single layer is small.
The present inventors have made extensive studies to achieve the above problems. As a result, an antistatic layer (B) containing a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) is formed on the base material layer (A) by using an extrusion coating method. The dispersibility of the polymer antistatic agent (B2) in the preventive layer (B) is improved, and as a result, even when the content of the polymer antistatic agent (B2) in the single layer is low. It has been found that a laminated film 10 having excellent antistatic properties can be obtained.
The reason why the dispersibility of the polymer-type antistatic agent (B2) in the antistatic layer (B) is improved by using the extrusion coating method is not clear, but it is used in Patent Document 1 when the extrusion coating method is used. It is considered that this is because the resin temperature at the time of molding can be raised as compared with the inflation film forming method used in the above.
That is, according to the method for producing the laminated film 10 according to the present embodiment, the resin composition (B3) is extruded and coated on the base material layer (A) to form an antistatic layer on the base material layer (A). By including the extrusion step of forming (B), the dispersibility of the polymer-type antistatic agent (B2) in the obtained antistatic layer (B) is improved, and the laminated film 10 having excellent antistatic properties can be obtained. Obtainable. Here, in the laminated film 10 according to the present embodiment, since the antistatic layer (B) which is an intermediate layer contains the polymer type antistatic agent (B2), the polymer type antistatic agent (B2) is a film. It is possible to suppress bleeding out to the outer surface. Further, since the laminated film 10 according to the present embodiment has excellent antistatic properties, dust and contents are heat-sealed when heat-sealing to form a bag or when filling a bag with contents. Adhesion to (C) and the base material layer (A) can be suppressed. As a result, the sealing properties of the obtained packaging material and the packaging body can be improved, and the reliability of the packaging material can be improved.
It is presumed that the morphology of the antistatic layer (B) having good dispersibility is different from that obtained by the inflation film forming method or the like, but it is difficult to specify the structure.

The method for producing the laminated film 10 according to the present embodiment is to extrude and coat a resin composition (B3) for forming an antistatic layer (B) on a base material layer (A) to form a base material layer. (A) includes an extrusion step of forming an antistatic layer (B) on the (A). The molding apparatus and molding conditions in this extrusion step are not particularly limited, and conventionally known molding apparatus and molding conditions can be adopted. As the molding apparatus, a T-die extruder or the like can be used. Further, as the molding conditions, the molding conditions of a known extrusion coating method can be adopted.

In the method for producing the laminated film 10 according to the present embodiment, the extrusion coating temperature in the extrusion step is appropriately set depending on the type and composition of the thermoplastic resin (B1) and the polymer antistatic agent (B2), and is not particularly limited. However, from the viewpoint of further improving the dispersibility of the polymer-type antistatic agent (B2) in the antistatic layer (B) and further improving the antistatic property of the obtained laminated film 10, the temperature is 200 ° C. or higher. It is preferably 250 ° C. or higher, more preferably 280 ° C. or higher.
The upper limit of the extrusion coating temperature in the extrusion step is not particularly limited, but is, for example, 350 ° C. or lower.

In the laminated film 10 according to the present embodiment, the attenuation time measured by the following method is preferably 1.0 second or less, more preferably 0.5 second or less, and further preferably 0.1 second or less. As a result, the antistatic property of the laminated film 10 can be further improved.
In the laminated film 10, the lower limit of the attenuation time of the laminated film 10 is not particularly limited, but is, for example, 0.0 seconds or more.
(Method)
FEDERAL TEST METHOD 101C METHOD 4046 (US federal government test standard), using an electrostatic voltage attenuation characteristic measuring device, under the conditions of applied voltage 5000V, 23 ° C, 50% RH, the above base material layer (A) A voltage is applied to the surface of the band until the band voltage reaches 5000 V, and then the time for the band voltage to decay from 5000 V to 500 V is measured, and this time is defined as the decay time.
In order to achieve such a decay time, the content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is set to 1% by mass or more and 10% by mass or less, and charging is performed by an extrusion coating method. It is particularly important to form the preventive layer (B).

Hereinafter, each layer constituting the laminated film 10 according to the present embodiment will be described.

<Base material layer (A)>
The base material layer (A) is a layer provided for the purpose of improving the handleability, mechanical properties, conductivity, heat insulating property, heat resistance, and other properties of the laminated film 10. Examples of the base material layer (A) include polyolefin films such as nylon films, polypropylene films, and polyethylene films, polyester films, polyamide films, polyimide films, polyvinylidene chloride films, ethylene / vinyl acetate copolymer films, and aluminum foils. Examples include aluminum vapor-deposited film and paper. These may be used individually by 1 type, or may be used in combination of 2 or more type. These may be uniaxially or biaxially stretched.
Among these, at least one selected from the group consisting of polyester film, nylon film and polyolefin film is preferable because it is excellent in mechanical strength, pinhole resistance and the like.

The thickness of the base material layer (A) is preferably 1 μm or more and 200 μm or less, more preferably 3 μm or more and 100 μm or less, and further preferably 5 μm or more and 80 μm or less from the viewpoint of obtaining good film characteristics.
The base material layer (A) may be surface-treated in order to improve the adhesiveness with other layers. Specifically, corona treatment, plasma treatment, anchor coating treatment, primer coating treatment and the like may be performed.

<Antistatic layer (B)>
The antistatic layer (B) according to the present embodiment is a resin composition (B3) containing a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). Is formed by.
The content of the thermoplastic resin (B1) in the antistatic layer (B) is 99% by mass or less from the viewpoint of improving the antistatic property when the entire antistatic layer (B) is 100% by mass. It is preferably 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, and particularly preferably 95% by mass or less, improving the transparency of the obtained laminated film 10 and suppressing the cost. From the viewpoint of the above, it is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, still more preferably 91% by mass or more, particularly preferably 92% by mass or more, and most preferably 94% by mass. % Or more.
Further, the content of the polymer type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass or less when the whole of the antistatic layer (B) is 100% by mass. , It is preferably 2% by mass or more and 10% by mass or less, but from the viewpoint of further improving the antistatic property, it is preferably 3% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more. From the viewpoint of improving the transparency of the obtained laminated film 10 and suppressing the cost, it is preferably 9% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.

The thickness of the antistatic layer (B) is, for example, 1 μm or more and 100 μm or less, preferably 3 μm or more and 80 μm or less, and particularly preferably 5 μm or more and 40 μm or less. From the viewpoint of the extrusion coating property of the antistatic layer (B), the thickness of the antistatic layer (B) is preferably 5 μm or more. From the viewpoint of price, the thickness of the antistatic layer (B) is preferably 40 μm or less.

Examples of the thermoplastic resin (B1) according to the present embodiment include high-density polyethylene, high-pressure low-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and other polyethylenes, and ethylene / unsaturated carboxylics. Acid-based copolymer, ethylene / unsaturated carboxylic acid ester-based copolymer, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl alcohol copolymer, ethylene / α-olefin copolymer elastomer, polypropylene, propylene Polypolymers (polymers of propylene and α-olefins other than propylene), polybutene, and other olefin-based (co) polymers, and polyolefins such as blends of these polymers; polyesters such as polyethylene terephthalate; 6- Examples thereof include polymers such as nylon and 6,6-nylon. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and the like.
Among these, polyolefin is used as the thermoplastic resin (B1) because it has an excellent balance of adhesiveness, handleability, bag making processability, price, etc. with the base material layer (A) and the heat-sealable layer (C). It is preferably contained, preferably low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene and propylene-based copolymer (copolymerization of propylene with α-olefin other than propylene). It is more preferable to contain at least one selected from the group consisting of (polymer).

The melt flow rate (hereinafter, also referred to as MFR) of the thermoplastic resin (B1) according to the present embodiment measured under the conditions of 190 ° C. and 2160 g load according to JIS K7210: 1999 is 0.1 g / 10 It is preferably minutes or more and 20 g / 10 minutes or less, more preferably 0.5 g / 10 minutes or more and 15 g / 10 minutes or less, and further preferably 1.0 g / 10 minutes or more and 10 g / 10 minutes or less. .. When the MFR is at least the above lower limit value, the workability of the antistatic layer (B) can be further improved. When the MFR is not more than the above upper limit value, a high shearing force can be applied to the resin composition (B3) containing the thermoplastic resin (B1) and the polymer antistatic agent (B2) in the extrusion coating step. As a result, the dispersibility of the polymer-type antistatic agent (B2) in the antistatic layer (B) can be further improved. As a result, the laminated film 10 having more excellent antistatic properties can be obtained.

Examples of the polymer type antistatic agent (B2) according to the present embodiment include ionomer resin, polyethylene oxide, polypropylene oxide, polyethylene glycol, polyesteramide, polyether esteramide, and polyether / polyolefin block copolymer (polyether). Block copolymers of based blocks and polyolefin-based blocks), quaternary ammonium salts such as polyethylene glycol methacrylate-based copolymers, and the like can be mentioned. These polymer-type antistatic agents (B2) may be used alone or in combination of two or more.
Among these, ionomer resin is preferable from the viewpoint of obtaining a laminated film 10 having more excellent antistatic properties.

Examples of the ionomer resin according to the present embodiment include ethylene-based ionomers, styrene-based ionomers, perfluorocarbon-based ionomers, and polyurethane-based ionomers. Among these, at least one selected from ethylene-based ionomers and styrene-based ionomers is preferable, and ethylene-based ionomers are more preferable.

Examples of the base resin of the ethylene-based ionomer include an ethylene / unsaturated carboxylic acid-based copolymer.
The ethylene / unsaturated carboxylic acid-based copolymer is a polymer obtained by copolymerizing at least ethylene and a monomer selected from unsaturated carboxylic acids as a copolymerization component, and if necessary, ethylene and unsaturated carboxylic acid. Monomers other than acid-based may be copolymerized.
The copolymer may be a block copolymer, a random copolymer, or a graft copolymer, but in consideration of productivity, a binary random copolymer, a ternary random copolymer, or a binary copolymer is used. It is preferable to use a graft copolymer of a random copolymer or a graft copolymer of a ternary random copolymer, and more preferably a binary random copolymer or a ternary random copolymer.
The ethylene / unsaturated carboxylic acid-based copolymer is selected from the group consisting of an ethylene / unsaturated carboxylic acid binary copolymer and an ethylene / unsaturated carboxylic acid alkyl ester / unsaturated carboxylic acid ternary copolymer. It is preferably at least one type.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, etaclilic acid, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, maleic acid, maleic anhydride, and maleic acid monoester (monomethyl maleate, monoethyl maleate). Etc.), maleic anhydride monoester (monomethyl maleic anhydride, monoethyl maleic anhydride, etc.) and other unsaturated carboxylic acids or half esters having 4 to 8 carbon atoms.
Among these, the unsaturated carboxylic acid preferably contains at least one selected from acrylic acid and methacrylic acid from the viewpoint of productivity of ethylene / unsaturated carboxylic acid-based copolymers. These unsaturated carboxylic acids may be used alone or in combination of two or more.

The ethylene-unsaturated carboxylic acid-based copolymer constituting the ethylene-based ionomer is at least a copolymer in which ethylene and an unsaturated carboxylic acid are copolymerized, and further, three or more elements in which a third copolymerization component is copolymerized. It may be a multiple copolymer of.

In the multiple copolymer, in addition to ethylene and (meth) acrylic acid copolymerizable with the ethylene, an unsaturated carboxylic acid ester (for example, methyl acrylate, ethyl acrylate, acrylic acid) as a third copolymerization component. Isobutyl, n-butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, (meth) acrylic acid alkyl esters such as dimethyl maleate, diethyl maleate), vinyl esters (eg, vinyl acetate, (Vinyl propionate, etc.), unsaturated hydrocarbons (eg, propylene, butene, 1,3-butadiene, penten, 1,3-pentadiene, 1-hexene, etc.), oxides such as vinyl sulfate and vinyl nitrate, halogen compounds (eg, vinyl sulfuric acid, vinyl nitrate, etc.) For example, vinyl chloride, vinyl fluoride, etc.), vinyl group-containing primary and secondary amine compounds, carbon monoxide, sulfur dioxide, etc. may be copolymerized.
Among these, as the third copolymerization component, an unsaturated carboxylic acid ester is preferable, and a (meth) acrylic acid alkyl ester (a preferable number of carbon atoms of the alkyl moiety is 1 to 4) is more preferable.

The content ratio of the constituent unit derived from the third copolymer component in the ethylene / (meth) acrylic acid-based copolymer is preferably in the range of 25% by mass or less.
When the content ratio of the constituent unit derived from the third copolymerization component is not more than the above upper limit value, it is preferable from the viewpoint of production and mixing.

In the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment, the structural unit derived from ethylene is preferably 65% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 92% by mass or less.
In the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment, the structural unit derived from the unsaturated carboxylic acid is preferably 5% by mass or more and 35% by mass or less, more preferably 8% by mass or more and 25% by mass or less. Is.

Examples of the styrene-based ionomer-based resin include a styrene / acrylic acid copolymer, a styrene / methacrylic acid copolymer, a styrene / maleic acid copolymer, a styrene / fumaric acid copolymer, and a styrene / maleic anhydride copolymer. Coalescence and the like can be mentioned. Among these, at least one selected from a styrene / acrylic acid copolymer and a styrene / methacrylic acid copolymer is preferable.

Examples of the metal ions constituting the ionomer resin according to the present embodiment include alkali metal ions such as lithium ions, potassium ions and sodium ions; and polyvalent metal ions such as calcium ions, magnesium ions, zinc ions, aluminum ions and barium ions. Can be mentioned. These metal ions may be used alone or in combination of two or more.
Among these, it is preferable to contain at least one selected from potassium ion, lithium ion and sodium ion, and it is more preferable to contain potassium ion.
Among ionomer resins, ionomer resins containing potassium ions as metal ions constituting the ionomer resin are preferable because they are approved for use in food applications.

The degree of neutralization of the ionomer resin according to the present embodiment is not particularly limited, but is preferably 95% or less, more preferably 90% or less, from the viewpoint of further improving processability and moldability.
The degree of neutralization of the ionomer resin according to the present embodiment is not particularly limited, but is preferably 10% or more, preferably 20%, from the viewpoint of further improving workability, antistatic property and heat resistance of the obtained laminated film 10. The above is more preferable, and 30% or more is further preferable.

The method for producing the ionomer resin is not particularly limited, and the ionomer resin can be produced by a known method. Further, as the ionomer resin, a commercially available one may be used.

In this embodiment, the melt flow rate (MFR) of the ionomer resin measured under the condition of 190 ° C. and 2160 g load according to JIS K7210: 1999 is 0.01 g / 10 minutes or more and 20 g / 10 minutes or less. It is preferably 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, and particularly preferably 0.1 g / 10 minutes or more and 5 g / 10 minutes or less. When the MFR is at least the above lower limit value, the workability of the antistatic layer (B) can be further improved. When the MFR is not more than the above upper limit value, a high shearing force can be applied to the resin composition (B3) containing the thermoplastic resin (B1) and the polymer antistatic agent (B2) in the extrusion coating step. As a result, the dispersibility of the polymer-type antistatic agent (B2) in the antistatic layer (B) can be further improved. As a result, the laminated film 10 having more excellent antistatic properties can be obtained.

The antistatic layer (B) can contain components other than the thermoplastic resin (B1) and the polymer-type antistatic agent (B2) as long as the object of the present invention is not impaired. The other components are not particularly limited, but are, for example, a plastic agent, an antioxidant, an ultraviolet absorber, an antistatic agent other than the polymer type antistatic agent (B2), a surfactant, a colorant, a light stabilizer, and foaming. Agents, lubricants, crystal nucleating agents, crystallization accelerators, crystallization retarders, catalyst deactivators, thermoplastic resins, thermosetting resins, inorganic fillers, organic fillers, impact resistance improvers, slip agents, Crosslinking agent, crosslinking aid, tackifier, silane coupling agent, processing aid, mold release agent, hydrolysis inhibitor, heat stabilizer, antiblocking agent, antifogging agent, flame retardant, flame retardant aid, light Diffusing agents, antibacterial agents, anti-crosslinking agents, dispersants, other resins and the like can be mentioned. The other components may be used alone or in combination of two or more, but from the viewpoint of adhesiveness and transparency, it is preferable that the slip agent is substantially not contained. Here, the fact that the slip agent is substantially not contained indicates that the content of the slip agent in the resin composition (B3) forming the antistatic layer (B) is 0.1% by mass or less.

<Heat sealable layer (C)>
The heat-sealable layer (C) is a layer for imparting heat-sealability to the laminated film 10 according to the present embodiment, and includes, for example, a thermoplastic resin (C1).
The thickness of the heat-sealing layer (C) is, for example, 1 μm or more and 300 μm or less, preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 150 μm or less.

Examples of the thermoplastic resin (C1) according to the present embodiment include high-density polyethylene, high-pressure low-density polyethylene, low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and other polyethylenes, and ethylene / unsaturated carboxylics. Acid-based copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-α-olefin copolymer elastomer, polypropylene, propylene-based copolymer (polymer of propylene and α-olefin other than propylene), Examples thereof include polybutene and other olefin-based (co) polymers, and polyolefins such as blends of these polymers. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene and the like.
Among these, it is preferable that the thermoplastic resin (C1) contains polyolefin from the viewpoint of excellent heat-sealing property, and low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ethylene / α-olefin copolymer weight. It is more preferable to contain at least one selected from the group consisting of a coalesced elastomer, polypropylene and a propylene-based copolymer (copolymer of propylene and α-olefin other than propylene).

The content of the thermoplastic resin (C1) in the heat-sealable layer (C) according to the present embodiment is preferably 50% by mass or more and 100% by mass when the entire heat-sealable layer (C) is 100% by mass. % Or less, more preferably 70% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less. As a result, the balance between the adhesiveness to the antistatic layer (B) and the heat sealability can be improved.

The heat-sealing layer (C) according to the present embodiment may contain a component other than the thermoplastic resin (C1) as long as the object of the present invention is not impaired. The other components are not particularly limited, but are, for example, a plasticizer, an antioxidant, an ultraviolet absorber, an antioxidant, a surfactant, a colorant, a light stabilizer, a foaming agent, a lubricant, a crystal nucleating agent, and crystallization. Accelerator, crystallization retarder, catalyst deactivator, thermoplastic resin other than thermoplastic resin (C1), thermocurable resin, inorganic filler, organic filler, impact resistance improver, slip agent, cross-linking agent, Crosslinking aid, tackifier, silane coupling agent, processing aid, mold release agent, hydrolysis inhibitor, heat stabilizer, antiblocking agent, antifogging agent, flame retardant, flame retardant aid, light diffusing agent, Examples thereof include antibacterial agents, anti-corrosion agents, dispersants and other resins. Other components may be used alone or in combination of two or more.

<Other layers>
The laminated film 10 according to the present embodiment may be composed of only three layers of a base material layer (A), an antistatic layer (B), and a heat-sealing layer (C), and the laminated film 10 may be various. From the viewpoint of imparting various functions, it may have layers other than the above three layers (hereinafter, also referred to as other layers). Examples of other layers include a foaming layer, a metal layer, an inorganic substance layer, a gas barrier layer, a hard coat layer, an adhesive layer, an antireflection layer, an antifouling layer, an anchor coat layer and the like. The other layers may be used alone or in combination of two or more layers.

<Use>
The laminated film 10 according to the present embodiment can be suitably used as a packaging material used for packaging foods, pharmaceuticals, industrial products, daily necessities, cosmetics and the like, and can be particularly preferably used as a food packaging material. can.

2. Packaging Material The packaging material according to the present embodiment includes at least a layer composed of the laminated film 10 according to the present embodiment. Further, the laminated film 10 according to the present embodiment may be used as a part of the packaging material according to the present embodiment, or the laminated film 10 according to the present embodiment may be used for the entire packaging material.
The shape of the packaging material according to the present embodiment is not particularly limited, and examples thereof include a sheet shape, a film shape, and a bag shape.
The bag-shaped form is not particularly limited, and examples thereof include a three-sided bag, a four-sided bag, a pillow bag, a gusset bag, and a stick bag.
The packaging material according to the present embodiment can be suitably used as a packaging material used for packaging foods, pharmaceuticals, industrial products, daily necessities, cosmetics, etc., and can be particularly preferably used as a food packaging material. ..

3. 3. Packaging body The packaging body according to the present embodiment includes the packaging material according to the present embodiment and the article packaged by the above-mentioned packaging material.
Examples of the above-mentioned articles include foods, pharmaceuticals, industrial products, daily necessities and the like.

Although the embodiments of the present invention have been described above with reference to the drawings, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
A laminated film in which the antistatic layer (B) is an extrusion coating processed layer formed by extrusion coating the resin composition (B3) on the base material layer (A).
2. It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
A laminated film having an attenuation time of 1.0 second or less, which is measured by the following method.
(Method)
In accordance with FEDERAL TEST METHOD 101C METHOD 4046 (US federal government test standard), the above base material layer (A) under the conditions of applied voltage of 5000 V, 23 ° C., and 50% RH using an electrostatic voltage attenuation characteristic measuring device. ) Is applied with a voltage until the band voltage reaches 5000 V, and then the time for the band voltage to decay from 5000 V to 500 V is measured, and this time is defined as the decay time.
3. 3. 2. In the laminated film described in
A laminated film in which the antistatic layer (B) is an extrusion coating processed layer.
4. 1. 1. To 3. In the laminated film according to any one of
Lamination in which the melt flow rate (MFR) of the thermoplastic resin (B1) is 0.1 g / 10 minutes or more and 20 g / 10 minutes or less as measured under the conditions of 190 ° C. and 2160 g load according to JIS K7210: 1999. the film.
5. 1. 1. To 4. In the laminated film according to any one of
A laminated film in which the thermoplastic resin (B1) contains polyolefin.
6. 1. 1. To 5. In the laminated film according to any one of
A laminated film having a thickness of the antistatic layer (B) of 5 μm or more.
7. 1. 1. To 6. In the laminated film according to any one of
A laminated film in which the polymer-type antistatic agent (B2) contains an ionomer resin.
8. 7. In the laminated film described in
A laminated film containing at least one selected from the group consisting of ethylene-based ionomers, styrene-based ionomers, perfluorocarbon-based ionomers, and polyurethane-based ionomers.
9. 8. In the laminated film described in
A laminated film in which the metal ions constituting the ionomer resin contain at least one selected from potassium ions, lithium ions, and sodium ions.
10. 1. 1. ~ 9. In the laminated film according to any one of
A laminated film in which the base material layer (A) contains at least one selected from the group consisting of a polyester film, a nylon film and a polyolefin film.
11. 1. 1. To 10. In the laminated film according to any one of
A laminated film in which the heat-sealing layer (C) contains polyolefin.
12. 1. 1. To 11. A packaging material comprising at least a layer composed of the laminated film according to any one of the above.
13. 12. A packaging body comprising the packaging material according to the above and an article packaged by the packaging material.
14. It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A method for producing a laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
A laminated film comprising an extrusion step of forming the antistatic layer (B) on the base material layer (A) by extrusion-coating the resin composition (B3) on the base material layer (A). Production method.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

The details of the materials used for producing the laminated film are as follows.

<Base material layer (A)>
PET1 (polyethylene terephthalate film, thickness: 12 μm)
PET2 (polyethylene terephthalate film, thickness: 50 μm)
ONy (biaxially stretched nylon film, thickness: 15 μm)
OPP (biaxially stretched polypropylene film, thickness: 20 μm)

<Antistatic layer (B)>
(Thermoplastic resin (B1))
LDPE1: Low density polyethylene (density: 923 kg / m ³ , MFR: 3.7 g / 10 minutes)
LDPE2: Low density polyethylene (density: 917 kg / m ³ , MFR: 7.2 g / 10 minutes)
LDPE3: Low density polyethylene (density: 917 kg / m ³ , MFR: 23 g / 10 minutes)

<Polymer antistatic agent (B2)>
IO-1: Ionomer of ethylene / methacrylic acid copolymer (ethylene content: 86% by mass, methacrylic acid content: 14% by mass, metal ion: potassium, neutralization degree: 84%, density: 965 kg / m ³ , MFR: 0.8g / 10 minutes)

<Heat sealable layer (C)>
LLDPE1 (low density polyethylene film, thickness: 30 μm)
LLDPE2 (low density polyethylene film, thickness: 100 μm)

[Examples 1 to 9 and Comparative Example 1]
A resin composition (B3) containing a thermoplastic resin (B1) and a polymer antistatic agent (B2) in the proportions shown in Table 1 is extruded between the base material layer (A) and the heat-sealing layer (C). By coating, an antistatic layer (B) was formed on the base material layer (A), and laminated films having a layer structure shown in Table 1 were obtained. The conditions for extrusion coating are as follows.
Extruder: 65 mmφ extruder (L / D = 28)
Extrusion coating temperature (temperature under die): 305 ° C, extrusion coating speed: 80 m / min, air gap: 110 mm
The surface of the base material layer (A) was previously subjected to an anchor coating treatment with an anchor coating agent.
The following evaluations were performed on the obtained laminated film. The results obtained are shown in Table 1.

<Evaluation of antistatic property>
The obtained laminated film was left at 40 ° C. for 2 days to cure the anchor coating agent. Next, the obtained laminated film was left to stand in an atmosphere of 23 ° C. and 50% RH for 7 days, and then, according to FEDERAL TEST METHOD 101C METHOD 4046 (US federal government test standard), an electrostatic voltage attenuation characteristic measuring device. (Electro-Tech Systems, Inc .: MODEL406D STTIC DECAY METER manufactured by ETS) was used on the surface of the laminated film on the substrate layer (A) side under the conditions of an applied voltage of 5000 V, 23 ° C., and 50% RH. The voltage was applied until the voltage reached 5000 V, and then the time (seconds) at which the band voltage decayed from 5000 V to 500 V was measured to evaluate the antistatic property of the laminated film. The MD direction of the laminated film was measured.

The laminated films of Examples 1 to 9 have an attenuation time of 1.0 second or less, and are excellent in antistatic properties even though the content of the polymer-type antistatic agent contained in the single layer is low. rice field. On the other hand, the laminated film of Comparative Example 1 had a long attenuation time and was inferior in antistatic property.

This application claims priority on the basis of Japanese application Japanese Patent Application No. 2018-014427 filed on March 8, 2018, and incorporates all of its disclosures herein.

Claims (10)

It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
A laminated film in which the antistatic layer (B) is an extrusion coating processed layer formed by extrusion coating the resin composition (B3) on the base material layer (A). It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
The antistatic layer (B) is an extrusion coating processed layer.
A laminated film having an attenuation time of 1.0 second or less, which is measured by the following method.
(Method)
In accordance with FEDERAL TEST METHOD 101C METHOD 4046 (US federal government test standard), the above base material layer (A) under the conditions of applied voltage of 5000 V, 23 ° C., and 50% RH using an electrostatic voltage attenuation characteristic measuring device. ) Is applied with a voltage until the band voltage reaches 5000 V, and then the time for the band voltage to decay from 5000 V to 500 V is measured, and this time is defined as the decay time. In the laminated film according to claim 1 or 2.
Lamination in which the melt flow rate (MFR) of the thermoplastic resin (B1) is 0.1 g / 10 minutes or more and 20 g / 10 minutes or less as measured under the conditions of 190 ° C. and 2160 g load according to JIS K7210: 1999. the film. In the laminated film according to any one of claims 1 to 3,
A laminated film having a thickness of the antistatic layer (B) of 5 μm or more. In the laminated film according to any one of claims 1 to 4.
Laminated film metal ion which constitutes the ethylene-based ionomer over is, containing at least one selected from potassium ion, lithium ion and sodium ion. In the laminated film according to any one of claims 1 to 5,
A laminated film in which the base material layer (A) contains at least one selected from the group consisting of a polyester film, a nylon film and a polyolefin film. In the laminated film according to any one of claims 1 to 6,
A laminated film in which the heat-sealing layer (C) contains polyolefin. A packaging material including at least a layer composed of the laminated film according to any one of claims 1 to 7. A packaging body comprising the packaging material according to claim 8 and an article packaged by the packaging material. It was formed of a resin composition (B3) containing at least a base material layer (A) and a thermoplastic resin (B1) and a polymer-type antistatic agent (B2) (excluding the thermoplastic resin (B1)). A method for producing a laminated film including an antistatic layer (B) and a heat-sealing layer (C) in this order.
The content of the polymer-type antistatic agent (B2) in the antistatic layer (B) is 1% by mass or more and 10% by mass, assuming that the entire antistatic layer (B) is 100% by mass. Is below
The thermoplastic resin (B1) is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ethylene / α-olefin copolymer elastomer, polypropylene, and a copolymer of polypropylene and α-olefin other than propylene. At least one selected from the group consisting of
The polymer-type antistatic agent (B2) is an ethylene-based ionomer using an ethylene / unsaturated carboxylic acid-based copolymer as a base resin.
A laminated film comprising an extrusion step of forming the antistatic layer (B) on the base material layer (A) by extrusion-coating the resin composition (B3) on the base material layer (A). Production method.

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