JPWO2020195713A1 - Laminates, packages, flexible container inner bags and flexible containers - Google Patents

Abstract

The resin layer A, the resin layer B, and the resin layer C are provided at least, and the resin layer B contains potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of 50% by mass or more of the entire resin layer B, and is a resin. The layer C is a laminate containing a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C.

Description

The present disclosure relates to laminates, packages, flexible container inner bags and flexible containers.

As a material for packaging such as bags and containers, polymer materials are widely used because of their light weight, high strength, and ease of processing. In general, a package made of a polymer material is easily charged, and dust in the air may adhere to the package at each stage of storage, transportation, and use, and the outer surface may be contaminated. In addition, the contents may adhere to the inner surface to spoil the appearance or deteriorate the quality of the contents. Further, since the electric insulation is large, static electricity is likely to be accumulated inside, and there is a concern that the static electricity may cause a disaster such as ignition of the contents.

As a method for suppressing the charge of a package made of a polymer material, for example, Japanese Patent Application Laid-Open No. 2003-226320 describes a container in which a surfactant is blended with a polymer material to control the surface resistivity within a specific range. It has been disclosed.

Japanese Patent Application Laid-Open No. 2003-226320 discusses charge suppression of a container made of a single-layer polymer material. However, when the container is composed of a plurality of layers, the static electricity charged in the contents cannot be sufficiently dissipated to the outside of the container due to reasons such as poor conductivity between the outer layer and the inner layer, and the inside of the container cannot be sufficiently dissipated. Static electricity may accumulate. As a result, the ignitable discharge phenomenon having a large discharge energy may not be sufficiently suppressed.

The present disclosure has been made in view of the above. According to one aspect of the present disclosure, a laminated body capable of producing a package in which static electricity does not easily accumulate inside, a package in which static electricity does not easily accumulate inside, a flexible container inner bag, and a flexible container are provided.

Specific means for solving the above problems include the following aspects.
<1> A resin layer A, a resin layer B, and a resin layer C are provided at least.
The resin layer B contains a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of 50% by mass or more of the entire resin layer B.
The resin layer C is a laminate containing an ethylene / unsaturated carboxylic acid copolymer potassium ionomer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C.
<2> The laminate according to <1>, wherein the thickness of the entire laminate is 120 μm or less.
<3> The laminate according to <1> or <2>, wherein the resin layer A, the resin layer B, and the resin layer C are arranged in this order.
<4> In an environment of 23 ° C. and a relative humidity of 50%, the surface resistivity of the surface of the laminated body opposite to the resin layer A when a voltage of 100 V is applied to the laminated body for 30 seconds is 1. The laminate according to any one of <1> to <3>, which is ^{x10 9} Ω / sq or more and 1 × 10 ^{12 Ω / sq or less.}
<5> The laminate according to any one of <1> to <4>, wherein the 1% attenuation time at an applied voltage of + 5000 V measured in an environment of 23 ° C. and a relative humidity of 50% on both sides is 1 second or less. ..
<6> The resin layer B contains two or more kinds of ethylene / unsaturated carboxylic acid copolymers of potassium ionomer having a difference between the maximum acid content and the minimum acid content of 2% by mass to 20% by mass, and the potassium of the potassium ionomer. The laminate according to any one of <1> to <5>, wherein the degree of neutralization by ions is 60% or more.
<7> The laminate according to any one of <1> to <6>, wherein the resin layer A contains an olefin polymer.
<8> The laminate according to any one of <1> to <7>, wherein the resin layer A contains linear low-density polyethylene.
<9> The laminate according to any one of <1> to <8>, wherein the resin layer A has a thickness of 20 μm or less.
<10> The method according to any one of <1> to <9>, wherein the resin layer A does not contain potassium ionomer, or when the resin layer A contains potassium ionomer, the amount thereof is 10% by mass or less of the whole resin layer A. Laminated body.
<11> In accordance with IEC 61340-4-4 (2005) and JIS C 61340-4-4 (2009), a laminate is used in an environment of 23 ° C. and a relative humidity of 50% using a dielectric breakdown tester. The laminate according to any one of <1> to <10>, wherein the voltage is increased at a rate of 0.3 kV per second, and the voltage when dielectric breakdown occurs is less than 4 kV. ..
<12> A package containing the laminate according to any one of <1> to <11>, wherein the resin layer A is arranged inside.
<13> The package according to <12>, further comprising an outer bag arranged on the outside of the laminated body.
<14> A flexible container inner bag containing the laminate according to any one of <1> to <11>, wherein the resin layer A is arranged inside.
<15> A flexible container including the flexible container inner bag according to <14> and an outer bag arranged outside the flexible container inner bag.

According to one aspect of the present disclosure, an object of the present disclosure is a laminate capable of producing a package in which static electricity does not easily accumulate inside, a package in which static electricity does not easily accumulate inside, a flexible container inner bag, and the like. Flexible containers are provided.

In the present disclosure, the numerical range indicated by using "~" indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the present disclosure, the amount of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. do.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. , May be replaced with the values shown in the examples.

<Laminated body>
The laminate of the present disclosure includes at least a resin layer A, a resin layer B, and a resin layer C, and the resin layer B contains a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of 50% by mass of the entire resin layer B. The resin layer C is a laminate containing the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C.

As a result of the examination by the present inventors, the dielectric breakdown voltage of the laminate having the above structure is sufficiently small, and the package manufactured by using this laminate has the insulation state easily destroyed and the static electricity accumulated inside. Was found to be able to escape to the outside. That is, the package manufactured by using the laminate of the present disclosure is excellent in safety because static electricity is less likely to be accumulated inside.

Further, the laminate of the present disclosure exerts a sufficient effect even if it does not contain an antistatic agent such as a surfactant or a conductive material such as carbon black. Therefore, for example, it is possible to prevent the antistatic agent from bleeding out to the surface of the laminated body and to prevent the flexibility and transparency from being lowered by blending the conductive material.

The ionomer in the present disclosure has a structure in which a part or all of the carboxylic acid groups contained in the base polymer are crosslinked by metal ions. More specifically, for example, "potassium ionomer of ethylene / unsaturated carboxylic acid copolymer" means that a part or all of the carboxylic acid groups contained in the ethylene / unsaturated carboxylic acid copolymer as a base polymer are potassium. It has a structure cross-linked by ions.

(Layer arrangement)
In the laminate, the resin layer A, the resin layer B, and the resin layer C are preferably arranged in this order.

It is preferable that the resin layer C is located outside the resin layer B (that is, at a position farther from the contents than the resin layer B) when the package is formed.

The resin layer B is preferably located outside the resin layer A (that is, at a position farther from the contents than the resin layer A) from the viewpoint of further suppressing the accumulation of static electricity inside the package.

(Thickness of laminated body)
The thickness of the entire laminate is not particularly limited, but is preferably 120 μm or less.
The thickness of the entire laminate is preferably 110 μm or less, and more preferably 100 μm or less, from the viewpoint of efficiently releasing static electricity to the outside.
From the viewpoint of durability, the thickness of the entire laminate is preferably 50 μm or more, and more preferably 60 μm or more.

(Characteristics of laminated body)
From the viewpoint of further suppressing the accumulation of static electricity inside the package, the laminate is used in an environment of 23 ° C. and a relative humidity of 50% when a voltage of 100 V is applied to the laminate for 30 seconds. The surface resistivity of the surface of the laminate opposite to the resin layer A is preferably 1 × 10 ⁸ Ω / sq or more and 1 × 10 ¹² Ω / sq or less, and 1 × 10 ⁹ Ω / sq or more and 1 ×. It is more preferably 10 ¹² Ω / sq or less, and further preferably 1 × 10 ⁹ Ω / sq or more and 9 × 10 ¹¹ Ω / sq or less.

The surface resistivity (Ω / sq) is 24 in an environment of 23 ° C. and 50% relative humidity using a high resistivity meter (for example, HIRESTA UP (MCP-HT450) manufactured by Mitsubishi Chemical Analytech Co., Ltd.). A laminated body test piece that has been allowed to stand for a long time is placed on a guard electrode, a ring-shaped electrode is brought into contact with the surface, and a voltage of 100 V is applied for 30 seconds.

The surface resistance is, for example, the ratio of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer, the degree of neutralization of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer, and each resin layer. It can be adjusted by adjusting the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer in the above.

From the viewpoint of further suppressing the accumulation of static electricity inside the package, the laminate has a 1% charge decay time of 1 second or less at an applied voltage of + 5000 V measured in an environment of 23 ° C. and 50% relative humidity on both sides. It is preferably 0.6 seconds or less, more preferably 0.4 seconds or less.

The 1% charge attenuation time is 23 ° C., and the laminate is allowed to stand for 24 hours in an environment of 50% relative humidity, and the charge attenuation measuring device (for example, Model 406D Voltage Meter manufactured by Electro-Tech Systems, Inc. of the United States) is used. The voltage + 5000V is applied, and the time during which the charge voltage applied to the test piece decays to + 50V is measured as the 1% charge decay time (sec) (according to the federal standard 101CMETHOD4046).

The 1% decay time is, for example, the ratio of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer, the degree of neutralization of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer, and each resin. It can be controlled by adjusting the content of the structural unit derived from the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer in the layer.

The laminate is relative to 23 ° C. in accordance with IEC 61340-4-4 (2005) and JIS C 61340-4-4 (2009) from the viewpoint of further suppressing the accumulation of static electricity inside the package. In an environment with a humidity of 50%, a dielectric breakdown tester is used to sandwich the laminate between electrodes, boost the voltage applied at a rate of 0.3 kV per second, and the voltage when dielectric breakdown occurs (that is, dielectric breakdown). The voltage) is preferably less than 4.0 kV, more preferably 3.5 kV or less, and even more preferably 3.0 kV or less. The lower limit of the dielectric breakdown voltage is not particularly limited, but is preferably 0.5 kV or more, for example.

The dielectric breakdown voltage is 0 per second when the laminate is sandwiched between electrodes using an insulation breakdown tester (for example, HAT-300-100RH0 type manufactured by Yamazaki Sangyo Co., Ltd.) in an environment of 23 ° C. and 50% relative humidity. It is obtained by boosting the voltage applied at a rate of 3 kV and measuring the voltage (kV) when dielectric breakdown occurs (IEC61340-4-4 (2005) and JIS C 61340-4-4 (2009). ) Compliant).

The insulation breakdown voltage is, for example, adjusting the proportion of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer; the degree of neutralization of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in each resin layer. To adjust the content of structural units derived from unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer in each resin layer; to adjust the thickness of the entire laminate; to adjust each resin. It can be adjusted by adjusting the thickness of the layer or the like.

(Resin layer A)
The resin layer A constituting the laminate contains a resin.
The resin contained in the resin layer A is not particularly limited and can be selected according to the properties required for the laminated body and the like. The resin contained in the resin layer A may be only one type or two or more types.

The resin contained in the resin layer A includes, for example, a homopolymer or copolymer of olefins, a polymer containing at least a structural unit derived from an olefin such as a polyolefin elastomer (hereinafter, also referred to as “olefin polymer”); Polymers containing at least styrene-derived structural units such as polystyrene, high-impact polystyrene, ABS (acrylonitrile-butadiene-styrene) resin (hereinafter, also referred to as "styrene-based polymers"); polyethylene terephthalate, polytrimethylene terephthalate, poly. Polyester such as tetramethylene terephthalate, polyethylene naphthalate, cyclohexanedimethanol copolymerized polyethylene terephthalate, polyester elastomer; acrylic resin such as polycarbonate and polymethylmethacrylate; polymer containing at least an amide bond such as polyamide and polyamide elastomer (hereinafter, "amide"). A thermoplastic resin such as "system polymer") can be mentioned.

The resin contained in the resin layer A preferably contains an olefin-based polymer from the viewpoint of heat-sealing properties, and may contain an ethylene-based polymer (a homopolymer of ethylene or a copolymer of ethylene and other components). More preferably, it contains a homopolymer of ethylene, a copolymer of ethylene and an α-olefin having 3 or more carbon atoms (preferably a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms), and ethylene. It is more preferable to contain at least one resin selected from the group consisting of a copolymer of and a polar monomer, and it is particularly preferable to contain linear low-density polyethylene.

Specific examples of the homopolymers of olefins include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear low-density polyethylene (LLDPE), and ultra-low-density polyethylene (VLDPE). Such as homopolymers of polyethylene; homopolymers of olefins other than polyethylene such as polypropylene, poly-1-butene, poly-4-methyl-1-pentene and the like can be mentioned.

Specifically, as a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4 Examples thereof include copolymers with α-olefins such as −methyl-1-pentene.

Specifically, as a copolymer of ethylene and a polar monomer, a copolymer of ethylene and vinyl acetate; a copolymer of ethylene and an unsaturated carboxylic acid (acrylic acid, methacrylic acid, monoethyl maleate, maleic anhydride, etc.) Polymers; with ethylene and unsaturated carboxylic acid esters (methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, -2-ethylhexyl acrylate, methyl methacrylate, glycidyl methacrylate, dimethyl maleate, etc.) Copolymers; Copolymers of ethylene, carbon monoxide and optionally unsaturated carboxylic acid esters or vinyl acetate; Copolymers of ethylene and polyolefin-based elastomers; These copolymers and Na, Li, Examples thereof include ionomers with Zn, Mg, Ca and the like.

From the viewpoint of antifouling property, the olefin polymer preferably contains an ethylene polymer produced in the presence of a metallocene catalyst.
As an example, the ethylene-based polymer can be produced by polymerizing ethylene and, if necessary, a copolymerization component used in the presence of a metallocene catalyst. The metallocene catalyst is, for example, a catalyst component composed of a compound of a transition metal (preferably zirconium) of Group IVB of the Periodic Table having at least one ligand having a cyclopentadienyl skeleton, and an organic aluminum oxy compound catalyst component. And various additive components used as needed.

The density of the ethylene-based polymer produced in the presence of the metallocene catalyst is not particularly limited and can be selected depending on the content of the copolymerization component (preferably α-olefin having 3 or more carbon atoms). In general, the density of the ethylene polymer ^may be a 870kg / ^{m 3} ~970kg / m 3 approximately, preferably ^{890kg / m 3 ~950kg / m 3} , more preferably 900kg ^/ m 3 ~940kg / M ³ .

From the viewpoint of processability and practical properties, the resin contained in the resin layer A preferably has a melt flow rate of 0.1 g / 10 minutes to 100 g / 10 minutes at 190 ° C. and a load of 2160 g, 0.2 g. It is more preferably / 10 minutes to 50 g / 10 minutes. In the present disclosure, the melt flow rate is measured according to JIS K7210-1 (2014).

The resin layer A may be composed of only the resin or may contain a component other than the resin. Examples of the components other than the resin include antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, lubricants, blocking inhibitors, inorganic fillers, foaming agents, foaming aids and the like. When the resin layer A contains a component other than the resin, the content thereof is preferably 10% by mass or less, and more preferably 5% by mass or less of the entire resin layer A.

The resin layer A does not contain potassium ionomer, or if it contains potassium ionomer, the amount thereof (that is, the amount of potassium ionomer) is preferably 10% by mass or less, preferably 5% by mass or less of the entire resin layer A. More preferably, it is more preferably 1% by mass or less.

The thickness of the resin layer A is not particularly limited. The thickness of the resin layer A is preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less, from the viewpoint of efficiently releasing static electricity to the outside. The thickness of the resin layer A is preferably 2 μm or more, and more preferably 5 μm or more, from the viewpoint of ensuring sufficient insulating properties.

(Resin layer B)
The resin layer B constituting the laminate contains the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in an amount of 50% by mass or more of the entire resin layer B.

The potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer contained in the resin layer B may be only one kind or two or more kinds.

The ethylene / unsaturated carboxylic acid copolymer used as the base polymer of the potassium ionomer is obtained by copolymerizing ethylene and unsaturated carboxylic acid, and other polar monomers used as needed.
The ethylene / unsaturated carboxylic acid copolymer is at least one 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 a seed.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, monomethyl maleate, and monoethyl maleate, and acrylic acid and methacrylic acid are preferable.

Examples of other polar monomers used as needed include vinyl esters such as vinyl acetate and vinyl propionate, unsaturated carboxylic acid esters, carbon monoxide and the like, and unsaturated carboxylic acid esters are particularly preferable.

Examples of the unsaturated carboxylic acid ester include an alkyl ester of an unsaturated carboxylic acid. As the alkyl ester of the unsaturated carboxylic acid, an alkyl ester having 2 to 5 carbon atoms of the unsaturated carboxylic acid is preferable, and an alkyl ester having 4 carbon atoms such as isobutyl and n-butyl of the unsaturated carboxylic acid is more preferable.

Among the alkyl esters of unsaturated carboxylic acids, alkyl esters of acrylic acid or methacrylic acid are preferable.
Specifically, examples of the alkyl ester of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, methyl methacrylate and ethyl methacrylate. Examples thereof include isobutyl methacrylate, n-butyl methacrylate, isooctyl methacrylate, dimethyl maleate and the like.
Among them, examples of the alkyl ester of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate and n methacrylate. -Lower alkyl esters of acrylic acid or methacrylic acid, such as butyl, isooctyl methacrylate (eg, alkyl esters with 2-5 carbon atoms) are preferred.
Further, as the alkyl ester of acrylic acid or methacrylic acid, an alkyl ester having 4 carbon atoms such as n-butyl ester of acrylic acid or methacrylic acid and an isobutyl ester is preferable, and an alkyl ester having 4 carbon atoms of acrylic acid (particularly preferable). Is more preferred.

The content of structural units derived from unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer (for example, the binary copolymer or the ternary copolymer) (hereinafter, "ethylene / unsaturated"). The "acid content of the carboxylic acid copolymer") is 10% by mass to 30% by mass with respect to the total amount of the ethylene / unsaturated carboxylic acid copolymer from the viewpoint of further suppressing the accumulation of static electricity. Is preferable, and it is more preferably 10% by mass to 25% by mass.

When the ethylene / unsaturated carboxylic acid copolymer is synthesized using ethylene, unsaturated carboxylic acid and other polar monomers, the ratio of the other polar monomers is relative to the total amount of the ethylene / unsaturated carboxylic acid copolymer. , 30% by mass or less, more preferably 15% by mass or less.

The degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer by potassium ions is preferably 60% or more, more preferably 70% or more from the viewpoint of further suppressing the accumulation of static electricity. Here, the degree of neutralization is the degree of loss of the carboxyl groups present in the ethylene / unsaturated carboxylic acid copolymer as the base polymer by the reaction with metal ions (based on the number of moles of the carboxyl groups). Indicated by%).

The melt flow rate of the ethylene / unsaturated carboxylic acid copolymer potassium ionomer at 190 ° C. and a load of 2160 g may be 0.1 g / 10 min to 100 g / 10 min from the viewpoint of processability, scratch resistance and the like. It is preferably 0.2 g / 10 minutes to 50 g / 10 minutes, more preferably.

From the viewpoint of further suppressing the accumulation of static electricity, the resin layer B preferably contains two or more kinds of ethylene / unsaturated carboxylic acid copolymers having potassium ionomers having different acid contents. For example, the resin layer B is a potassium ionomer of two or more kinds of ethylene / unsaturated carboxylic acid copolymers in which the difference between the maximum acid content and the minimum acid content is 1% by mass or more, preferably 2% by mass to 20% by mass. It is preferable to include. The maximum acid content refers to the acid content of the potassium ionomer having the highest acid content among the potassium ionomers of two or more kinds of ethylene / unsaturated carboxylic acid copolymers. On the other hand, the minimum acid content refers to the acid content of the potassium ionomer having the lowest acid content among the potassium ionomers of two or more kinds of ethylene / unsaturated carboxylic acid copolymers.
In this case, the acid content (average acid content) of the two or more kinds of ethylene / unsaturated carboxylic acid copolymers is preferably 10% by mass to 30% by mass, preferably 10% by mass to 25% by mass. Is more preferable.
In this case, the lower limit of the neutralization degree of the entire potassium ionomer of the two or more kinds of ethylene / unsaturated carboxylic acid copolymers by potassium ions is preferably 60% or more, more preferably 70% or more. The upper limit of the neutralization degree of the entire potassium ionomer of two or more kinds of ethylene / unsaturated carboxylic acid copolymers by potassium ions is not particularly limited, but is preferably 90% or less, for example.

As a combination of two or more kinds of ethylene / unsaturated carboxylic acid copolymers having different acid contents as the base polymer, for example, the acid content is 1% by mass to 11% by mass, preferably 2% by mass to 10% by mass. , 190 ° C., an ethylene / unsaturated carboxylic acid copolymer (A-1) having a melt flow rate of 1 g / 10 min to 600 g / 10 min, preferably 10 g / 10 min to 500 g / 10 min under a load of 2160 g. The acid content is 11% by mass to 25% by mass, preferably 13% by mass to 23% by mass, and the melt flow rate at 190 ° C. and a load of 2160 g is 1 g / 10 minutes to 600 g / 10 minutes, preferably 10 g / 10 minutes to. It is a combination with an ethylene / unsaturated carboxylic acid copolymer (A-2) having a weight of 500 g / 10 minutes, and has an average acid content of 10% by mass to 20% by mass, preferably 11% by mass to 15% by mass. The average melt flow rate under a load of 190 ° C. and 2160 g is 1 g / 10 min to 300 g / 10 min, preferably 10 g / 10 min to 200 g / 10 min, and more preferably 20 g / 10 min to 150 g / 10 min. Suitable.

In the above combination, the mixing ratio of the copolymer (A-1) and the copolymer (A-2) is, for example, 100 parts by mass of the former and 1 part by mass to 200 parts by mass, preferably 50 parts by mass of the latter. It may be a part to 150 parts by mass.

The resin layer B may be composed of only the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer, or may contain a component other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer (however, it may be contained). The amount of potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer is 50% by mass or more of the entire resin layer B). The resin layer B may contain a resin other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer, for example, as long as the antistatic performance, slipperiness and scratch resistance of the laminate are not significantly impaired.

The type of resin other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer is not particularly limited, and may be selected from those exemplified as the resin contained in the resin layer A. As the resin other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer, an olefin polymer is preferable, an ethylene polymer is more preferable, and an ethylene homopolymer, ethylene and carbon are preferable from the viewpoint of heat sealability. At least one selected from the group consisting of a polymer of α-olefin having a number of 3 or more (preferably 3 to 12 carbon atoms) and a polymer of ethylene and a polar monomer is more preferable, and linear low density is more preferable. Polyethylene is particularly preferred.

When the resin layer B contains a resin other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer, the proportion of the resin other than the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer is 45% by mass of the entire resin layer B. It may be less than or equal to, 35% by mass or less, and 25% by mass or less. That is, the proportion of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer may be 55% by mass or more, 65% by mass or more, or 75% by mass or more of the entire resin layer B. May be good.

The resin layer B may contain a polyhydroxy compound having two or more alcoholic hydroxyl groups in order to improve the antistatic performance. Specific examples of the polyhydroxy compound include polyoxyalkylene glycols having various molecular weights such as polyethylene glycol, polypropylene glycol, and polyoxyethylene / polyoxypropylene glycol; polyhydric alcohols such as glycerin, hexanetriol, pentaerythritol, and sorbitol; and these. Ethethylene oxide adducts; polyhydric amine and alkylene oxide adducts and the like can be exemplified.

When the resin layer B contains a polyhydroxy compound, the amount of the polyhydroxy compound is preferably set within a range that does not impair the mechanical properties of the resin layer B. For example, the amount of the polyhydroxy compound may be 15% by mass or less of the entire resin layer B or 10% by mass or less.

The resin layer B may contain an antioxidant, a light stabilizer, an ultraviolet absorber, a pigment, a dye, a lubricant, an antiblocking agent, an inorganic filler, a foaming agent, a foaming aid and the like, if necessary. When the resin layer B contains these components, the amount thereof is preferably 10% by mass or less, more preferably 5% by mass or less of the entire resin layer B.

The thickness of the resin layer B is not particularly limited. The thickness of the resin layer B may be selected from the range of 20 μm to 90 μm from the viewpoint of efficiently releasing static electricity to the outside.

(Resin layer C)
The resin layer C constituting the laminate contains the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C.
The resin contained in the resin layer C may be only one type or two or more types.

Details and preferred embodiments of the components contained in the resin layer C (resin, potassium ionomer of ethylene / unsaturated carboxylic acid copolymer and other components) are detailed and preferred embodiments of the components contained in the resin layer A and the resin layer B. Is the same as.

The amount of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer contained in the resin layer C may be more than 10% by mass and less than 50% by mass of the entire resin layer C. For example, the amount of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer contained in the resin layer C may be more than 10% by mass and 40% by mass or less of the whole resin layer C, and may be more than 10% by mass. It may be 30% by mass or less, and may be more than 10% by mass and 25% by mass or less.

The amount of the potassium ionomer of the ethylene / unsaturated carboxylic acid copolymer contained in the resin layer C is preferably 15% by mass or more, preferably 20% by mass or more, from the viewpoint of efficiently releasing static electricity to the outside. % Or more is more preferable.

The thickness of the resin layer C is not particularly limited. The thickness of the resin layer C may be selected from the range of 1 μm to 20 μm from the viewpoint of efficiently releasing static electricity to the outside.

(Other parts)
The laminate of the present disclosure may be composed of only the resin layers A, B and C described above, or may include members other than the resin layers A, B and C. However, from the viewpoint of lowering the dielectric breakdown voltage, it is preferable that the members other than the resin layers A, B and C are not provided.
In the laminate of the present disclosure, for example, an adhesive layer containing a rubber-based adhesive material, an acrylic-based adhesive material, a silicon-based adhesive material, or the like may be further provided in order to bring the resin layers into close contact with each other. Alternatively, the laminate of the present disclosure may be further provided with a barrier layer for enhancing the gas barrier property and the water vapor barrier property of the laminate. As the barrier layer, a stretched film of polyethylene terephthalate (PET), polyamide, polyolefin, etc., and a thin film of an inorganic compound such as aluminum, aluminum oxide, silicon oxide, etc. on these stretched films are physically vapor-deposited or chemically vapor-deposited to about 20 nm to 100 nm. Inorganic compound vapor-deposited plastic film, aluminum foil, ethylene vinyl alcohol copolymer resin film, vinylidene chloride film, polyvinyl alcohol film and the like provided to have a thickness can be preferably used. The adhesive layer and the barrier layer may be used by laminating them, if necessary.

When the laminate includes members other than the resin layers A, B, and C, the thickness of the laminate is the thickness including the thickness of these members.

The method for producing the laminate of the present disclosure is not particularly limited, and a conventionally known method can be adopted. For example, the laminate of the present disclosure can be produced by laminating each layer by a molding method such as extrusion coating molding, coextrusion molding, multi-layer inflation molding, sandwich laminating molding or the like.

<Packaging>
The package of the present disclosure includes the laminate of the present disclosure, and the resin layer A is arranged inside (the side closer to the contents). The shape and size of the package are not particularly limited, and bags, containers, etc. of any shape and size may be used.

The package may be composed of only the laminate or may include members other than the laminate. For example, the packaging may include an outer bag that is located outside the laminate. The material of the outer bag is not particularly limited, but from the viewpoint of efficiently releasing static electricity inside, it is preferable to use a material having conductivity.

The use of the package is not particularly limited, but it is particularly preferably used as an inner bag of a flexible container. Flexible containers generally have a large capacity, and there is a high risk of accidents due to static electricity accumulated inside. Therefore, the flexible container provided with the package made from the laminate of the present disclosure, in which static electricity is less likely to be accumulated inside, is excellent in safety.

<Flexible container inner bag and flexible container>
The flexible container inner bag of the present disclosure includes the laminate of the present disclosure, and the resin layer A is arranged inside (the side closer to the contents).
The flexible container of the present disclosure includes the flexible container inner bag and an outer bag arranged outside the flexible container inner bag.
The capacity of the flexible container inner bag or the flexible container is not particularly limited, and may be, for example, 100 liters to 1000 liters.

Hereinafter, the present disclosure will be described in more detail with reference to Examples, but the present disclosure is not limited to these Examples. In the following Examples and Comparative Examples, the performance evaluation methods and results of the raw materials used and the obtained laminate are shown below. The melt flow rate (MFR) was measured at 190 ° C. and a load of 2160 g according to JIS K7210-1 (2014).

<Manufacturing of laminated body>
The potassium ionomers (IO-1 and IO-2) shown in Table 2 were synthesized from the base polymers shown in Table 1 as raw materials. The amount of glycerin added shown in Table 2 is the content ratio with respect to the entire potassium ionomer.

As the resin other than the potassium ionomer contained in the resin layer, the thermoplastic resin shown in Table 3 was used.

[Examples 1 to 4 and Comparative Examples 1 to 5]
Using the above-mentioned materials, a laminate having the constitution shown in Table 4 was prepared. Specifically, using a multilayer inflation film molding machine, MPE-1 is a resin layer A (inner layer), IO-1 is a resin layer B (intermediate layer), MPE-1 (80 parts by mass) and IO-1 (80 parts by mass). The mixed resin dry-blended at a blending ratio of 20 parts by mass) was configured to be the resin layer C (outer layer), and the molding temperature (die temperature) was set to 170 ° C. to prepare the laminate of Example 1. Further, the laminates of Examples 2 to 4 and Comparative Examples 1 to 5 were obtained in the same manner as in Example 1 except that the composition and thickness of the resin layer and the molding temperature were changed as shown in Table 4 (Comparative Example 4). Used a single-layer inflation film molding machine).

<Evaluation of electrical characteristics of laminated body>
The electrical characteristics of the prepared laminate were evaluated by the following tests. The "evaluation of the electrical characteristics of the inner surface" shown in Table 4 is the evaluation of the surface of the resin layer A, and the "evaluation of the electrical characteristics of the outer surface" is the evaluation of the resin layer C when the laminate includes the resin layer C. When the laminate is provided with the resin layer B and is not provided with the resin layer C, the surface of the resin layer B is evaluated, and when the resin layer A is used alone, the other surface of the resin layer A is evaluated. be.

(1) In an environment where the dielectric breakdown voltage is 23 ° C. and the relative humidity is 50%, the laminate is sandwiched between electrodes using the dielectric breakdown tester "HAT-300-100RH0 type" manufactured by Yamazaki Sangyo Co., Ltd. The voltage applied was increased at a rate of 3 kV, and the voltage (kV) when dielectric breakdown occurred was measured (according to IEC61340-4-4 (2005) and JIS C 61340-4-4 (2009)).

(2) A laminated body left to stand for 24 hours in an environment with a 1% charge decay time of 23 ° C. and a relative humidity of 50% was subjected to a voltage of +5000 V using a "Model 406D Static Device Meter" manufactured by Electro-Tech Systems of the United States. Was applied, and the time during which the charge voltage applied to the test piece decayed to + 50 V was measured as the 1% charge decay time (sec) (according to the federal standard 101CMETHOD4046).

(3) Surface resistivity Laminating using a high resistivity meter "HIRESTA UP (MCP-HT450)" manufactured by Mitsubishi Chemical Analytech Co., Ltd., and allowing it to stand for 24 hours in an environment of 23 ° C. and 50% relative humidity. The body test piece was placed on a guard electrode, a ring-shaped electrode was brought into contact with the surface, a voltage of 100 V was applied for 30 seconds, and the surface resistivity (Ω / sq) was measured.

As shown in Table 4, the resin layer A, the resin layer B, and the resin layer C are provided at least, and the resin layer B contains potassium ionomer in an amount of 50% by mass or more of the entire resin layer B, and the resin layer C is formed. The laminate of Examples containing potassium ionomer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C achieved a lower breakdown voltage than that of the laminate of Comparative Example.
Further, in the laminated body of the example, (1) the surface resistivity of the outer surface is 1 × 10 ⁹ Ω / sq or more and 1 × 10 ¹² Ω / sq or less, and (2) the surface resistivity of the inner surface is 1 × 10 ¹² It showed the electrical characteristics conforming to the standard (L2) of the FIBC inner bag standard (IEC 61340-4-4 (2018)) that the voltage was more than Ω / sq and (3) the breakdown voltage was less than 4 kV.

In Comparative Example 1 having the resin layer A and the resin layer C but not the resin layer B, and Comparative Examples 2 and 3 having the resin layer A and the resin layer B but not the resin layer C, the insulation is provided. The breakdown voltage was over 5 kV.
In Comparative Examples 4 and 5 in which the resin layer A alone having a thickness of 50 μm or 110 μm was evaluated, when a voltage of 5000 V was applied to the sample, it was not charged by 4500 V or more, and the 1% charge decay time could not be measured. Further, in Comparative Examples 4 and 5, the dielectric breakdown voltage was also large.

The embodiments of the present disclosure also include the following aspects.
[1] A resin layer A and a resin layer B are provided at least, and the thickness is 100 μm or less.
The resin layer B is a laminate containing an ethylene / unsaturated carboxylic acid copolymer potassium ionomer in an amount of 50% by mass or more of the entire resin layer B.
[2] The laminate according to [1], further comprising a resin layer C, wherein the resin layer C contains a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of less than 50% by mass of the entire resin layer C.
[3] The laminate according to [2], wherein the resin layer A, the resin layer B, and the resin layer C are arranged in this order.
[4] In an environment of 23 ° C. and a relative humidity of 50%, the surface resistivity of the surface of the laminated body opposite to the resin layer A when a voltage of 100 V is applied to the laminated body for 30 seconds is 1. The laminate according to any one of [1] to [3], which is ^{x10 9} Ω / sq or more and 1 × 10 ^{12 Ω / sq or less.}
[5] The laminate according to any one of [1] to [4], wherein the 1% attenuation time at an applied voltage of + 5000 V measured in an environment of 23 ° C. and a relative humidity of 50% on both sides is 1 second or less. ..
[6] The resin layer B contains two or more kinds of ethylene / unsaturated carboxylic acid copolymers of potassium ionomer having a difference between the maximum acid content and the minimum acid content of 2% by mass to 20% by mass, and the potassium of the potassium ionomer. The laminate according to any one of [1] to [5], wherein the degree of neutralization by ions is 60% or more.
[7] The laminate according to any one of [1] to [6], wherein the resin layer A contains an olefin polymer.
[8] The laminate according to any one of [1] to [7], wherein the resin layer A contains linear low-density polyethylene.
[9] The laminate according to any one of [1] to [8], wherein the resin layer A has a thickness of 20 μm or less.
[10] The method according to any one of [1] to [9], wherein the resin layer A does not contain potassium ionomer, or when the resin layer A contains potassium ionomer, the amount thereof is 10% by mass or less of the whole resin layer A. Laminated body.
[11] In accordance with IEC 61340-4-4 (2005) and JIS C 61340-4-4 (2009), a laminate is used in an environment of 23 ° C. and a relative humidity of 50% using a dielectric breakdown tester. The laminate according to any one of [1] to [10], wherein the voltage is increased at a rate of 0.3 kV per second, and the voltage when dielectric breakdown occurs is less than 4 kV. ..
[12] A package containing the laminate according to any one of [1] to [11], wherein the resin layer A is arranged inside.
[13] The package according to [12], further comprising an outer bag arranged on the outside of the laminate.
[14] A flexible container inner bag containing the laminate according to any one of [1] to [11] and in which the resin layer A is arranged inside.
[15] A flexible container comprising the flexible container inner bag according to [14] and an outer bag arranged outside the flexible container inner bag.

Claims (15)

A resin layer A, a resin layer B, and a resin layer C are provided at least.
The resin layer B contains a potassium ionomer of an ethylene / unsaturated carboxylic acid copolymer in an amount of 50% by mass or more of the entire resin layer B.
The resin layer C is a laminate containing an ethylene / unsaturated carboxylic acid copolymer potassium ionomer in an amount of more than 10% by mass and less than 50% by mass of the entire resin layer C. The laminate according to claim 1, wherein the thickness of the entire laminate is 120 μm or less. The laminate according to claim 1 or 2, wherein the resin layer A, the resin layer B, and the resin layer C are arranged in this order. The surface resistivity of the surface of the laminated body opposite to the resin layer A when a voltage of 100 V is applied to the laminated body for 30 seconds in an environment of 23 ° C. and a relative humidity of 50% is 1 × 10 ^9. The laminate according to any one of claims 1 to 3, wherein the laminate is Ω / sq or more and 1 × 10 ^{12 Ω / sq or less.} The laminate according to any one of claims 1 to 4, wherein the 1% attenuation time at an applied voltage + 5000 V measured in an environment of 23 ° C. and a relative humidity of 50% on both sides is 1 second or less. The resin layer B contains two or more kinds of ethylene / unsaturated carboxylic acid copolymers having a potassium ionomer having a difference between the maximum acid content and the minimum acid content of 2% by mass to 20% by mass, and is contained in the potassium ionomer of the potassium ionomer. The laminate according to any one of claims 1 to 5, wherein the sum is 60% or more. The laminate according to any one of claims 1 to 6, wherein the resin layer A contains an olefin polymer. The laminate according to any one of claims 1 to 7, wherein the resin layer A contains linear low-density polyethylene. The laminate according to any one of claims 1 to 8, wherein the thickness of the resin layer A is 20 μm or less. The laminate according to any one of claims 1 to 9, wherein the resin layer A does not contain potassium ionomer, or if the resin layer A contains potassium ionomer, the amount thereof is 10% by mass or less of the whole resin layer A. In accordance with IEC 61340-4-4 (2005) and JIS C 61340-4-4 (2009), the laminate is electrode-loaded using a dielectric breakdown tester in an environment of 23 ° C. and 50% relative humidity. The laminate according to any one of claims 1 to 10, wherein the voltage applied by sandwiching and applying at a rate of 0.3 kV per second is boosted, and the voltage when dielectric breakdown occurs is less than 4 kV. A package body comprising the laminate according to any one of claims 1 to 11, wherein the resin layer A is arranged inside. The package according to claim 12, further comprising an outer bag arranged on the outside of the laminate. A flexible container inner bag containing the laminate according to any one of claims 1 to 11 and in which the resin layer A is arranged inside. A flexible container comprising the flexible container inner bag according to claim 14 and an outer bag arranged outside the flexible container inner bag.