KR100732027B1 - Multi-layer structure with potassium ionomer - Google Patents

Abstract

The present invention comprises at least two layers comprising a potassium ionomer layer (X) having a low surface resistivity and a layer (Y) having an improved electrostatic charge attenuation characteristic, which is made of a polymer material having a high surface resistivity such as LLDPE as a surface layer. It relates to a multilayer structure. This two- or three-layer structure of this type, with layer (X) as its intermediate or other surface layer, is excellent in slipping, abrasion resistance, and antifouling property, and thus is useful as a packaging material such as films, sheets and containers.

Multi-layered structure, potassium ionomer.

Description

MULTI-LAYER STRUCTURE WITH POTASSIUM IONOMER

The present invention relates to a multilayer structure (laminate) having at least one potassium ionomer layer excellent in charge decay characteristics, slip characteristics, abrasion resistance, and the like. In particular, the present invention relates to a multilayer structure having excellent processability, mechanical properties, and antifouling properties suitable for molding materials such as packaging.

Olefin polymers are widely used in the field of general packaging films. Among them, ethylene polymers are most commonly used because of their excellent heat sealability. Although excellent slip resistance is required in the manufacturing process of the film and excellent scratch resistance is required in terms of the performance of the film, general purpose ethylene polymers having both of these properties are rare. For example, adding a slip agent to polyethylene having a wide range of densities results in sufficient slip resistance, but this does not exhibit satisfactory scratch resistance. Although general purpose ionomers are inherently excellent in scratch resistance, slip properties are insufficient.

In general, molded articles made of polymeric materials easily generate static electricity and attract dust from the air during storage, transportation, and handling in end use, resulting in contamination of the surface of the molded article. In the case where the molded article is a bag such as powder, a part of the contained powder adheres to the inner surface of the bag, which damages the appearance of the package and impairs the commercial value of the product. In order to prevent the adhesion of dust and powder, various antistatic technologies have been proposed and put into practice. Among the approaches generally employed, there are a method of melt-blending an antistatic agent in a molding resin composition and a method of coating a molded article with an antistatic agent or an antistatic polymer. However, these methods are known to have some drawbacks. For example, in the former method, the bleed out of the migrated antistatic agent often involves the contamination of the packaged material, or the problem that the antistatic effect deteriorates with time. In the latter method, defects such as poor water resistance of the coating film, damage to the coating film, or increase in surface tackiness due to absorption of moisture are pointed out.

In order to ameliorate the aforementioned drawbacks of the method of coating an antistatic agent or an antistatic polymer, another surface layer is further provided on the antistatic polymer layer for the purpose of blanketing the antistatic polymer layer. Some attempts have been made. For example, Japanese Unexamined Patent Application Publication No. 2 (1990) -28919 discloses a plastic base material and an ionic conductive resin layer thereon, and a water resistance plastic having a volume resistivity of 1 × 10 ¹³ Pa · cm or less and a thickness of 10 μm or less. A layered antistatic plastic film is proposed. According to this proposal, usable materials are limited and it is difficult to obtain a laminated film having various characteristics.

Japanese Patent Application Laid-Open No. 61 (1986) -44646 discloses a multilayer structure without static electricity and bleed-out, having an alkali metal salt or an amine salt of an ethylene-unsaturated carboxylic acid copolymer as an intermediate layer. In addition, Japanese Patent Application Laid-Open No. 10 (1998) -193495 discloses a potassium ionomer and a polyhydroxy compound of an ethylene-unsaturated carboxylic acid copolymer in order to improve the antistatic effect under the low humidity of the above publication. A dust-free multilayer structure having an intermediate layer has been proposed. The comparative example shows that the antistatic property was insufficient in the multilayer structures according to the above publication technique.

The present inventors have diligently studied to obtain a material having excellent heat sealing, antifouling, slip, and scratch resistance suitable as a packaging material, and found that a particular multilayer structure has excellent performance in all of the above. Furthermore, the inventors have found that by selecting a suitable polymer as the surface layer, as described later, the specific multilayer structure exhibits excellent antifouling properties without adding a polyhydroxy compound.

Accordingly, an object of the present invention is to provide an antifouling multilayer structure which is excellent in antifouling property, slip resistance, scratch resistance, and the like, and which can prevent electrostatic adhesion of dust, powder and the like.

Disclosure of the Invention

The present invention provides a layer (layer (X)) of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of the potassium ionomer and a thermoplastic polymer, and a layer made of a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more ( Layer (Y)), comprising at least two layers, wherein the at least one surface layer has a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less, It is to provide a multilayer structure.

One preferred aspect of the present invention is a layer (X) made of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of the potassium ionomer and a thermoplastic polymer, and a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more. Consisting of two layers comprising at least one surface layer (Y), wherein the layer (Y) has a 10% charge decay time of 20% at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity. It is a multilayer structure which is less than a second.

In this preferred embodiment, the layer (X) occupies the position of the other surface layer of the structure, and both surface layers have a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity. It is preferable that it is 20 second or less. Such multi-layered structures are suitable for the purpose of films, sheets for packaging, decorative or automotive exterior or interior use, blow molded containers and the like. Especially, the structure whose friction coefficient is 1 or less is preferable. Structures of this type are suitably used for bags and multilayer containers.

In one preferred aspect, the multilayer structure consists of at least three layers, wherein (a) layer (X) points to the position of the intermediate layer and the other surface layer (Z) is made of a polymeric material having a surface resistivity of 1 × 10 ¹⁴ Ω or more. (B) The surface layer (Y) has a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less, and (c) the surface layer (Z) is also 23 ° C. , It is preferable that the 10% charge decay time at the applied voltage +5000 V measured in an atmosphere of 50% relative humidity is 20 seconds or less. Multilayer structures of this type are useful for applications including films, sheets, bags and multilayer containers.

Preferred Aspects of the Invention

In the structure of the present invention, the layer (X) forming one surface layer or intermediate layer is composed of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of the potassium ionomer and a thermoplastic polymer. The surface resistivity of the layer (X) is not limited, but is preferably in the range of 1 × 10 ¹² Ω or less, more preferably 1 × 10 ¹¹ Ω or less, still more preferably 1 × 10 ¹⁰ Ω or less. The ethylene-unsaturated carboxylic acid copolymer used as the base polymer of the potassium ionomer of the layer (X) is obtained by copolymerizing ethylene with an unsaturated carboxylic acid and optionally another polar monomer.

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, monomethyl maleate and monoethyl maleate. Acrylic acid or methacrylic acid is particularly preferred. In addition, as another polar monomer which can be used as a copolymerization component, Vinyl ester, such as vinyl acetate and vinyl propionate; Unsaturated carboxyl such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, dimethyl maleate, diethyl maleate Acid esters; Carbon monoxide etc. are mentioned. In particular, unsaturated carboxylic esters are suitable as copolymerization components. The said ethylene-unsaturated carboxylic acid copolymer can be obtained by radical copolymerization of ethylene and an unsaturated carboxylic acid with other arbitrary polar monomers at high temperature and high pressure.

When the acid content of the ethylene-unsaturated carboxylic acid copolymer used as the base polymer of potassium ionomer is extremely small or the neutralization degree of the potassium ionomer is extremely low, the antifouling property is excellent and 10% at an applied voltage of +5000 V. A multilayer structure having the surface layer Y whose charge decay time is a desired value cannot be obtained. Therefore, the unsaturated carboxylic acid content of the base ethylene-unsaturated carboxylic acid copolymer (or the average unsaturated carboxylic acid content of the base ethylene-unsaturated carboxylic acid copolymer) is 10 to 30% by weight, preferably 10 to 25% by weight. % Or one or two potassium ionomers of the ethylene-unsaturated carboxylic acid copolymer having a degree of neutralization by potassium of 60% or more (60-100%), preferably 70% or more (70-100%). It is preferable to use more than one type. In order to obtain a multilayer structure having excellent antifouling property in the present invention, it is preferable to use a mixture of potassium ionomers of two or more kinds of ethylene-unsaturated carboxylic acid copolymers having different average acid contents. For example, two or more copolymers having an average carboxylic acid content of 10 to 30% by weight, preferably 10 to 20% by weight, wherein the average acid content is different, that is, the difference between the highest content and the lowest content is 1 It is a mixed ionomer having a degree of neutralization by potassium ions of at least 60% by weight, preferably 2 to 20% by weight, of ethylene-unsaturated carboxylic acid copolymer. More specifically, the average unsaturated carboxylic acid content is 10 to 30% by weight, preferably 10 to 20% by weight, and the average melt flow rate measured at 190 ° C. under a load of 2160 g is 1 to 300 g / 10 minutes. Particularly preferred are mixed ionomers having the above-mentioned degree of neutralization (60% or more) of the mixed copolymer composition, preferably 10 to 200 g / 10 minutes, more preferably 20 to 150 g / 10 minutes. This mixed ionomer preferably has an unsaturated carboxylic acid content of 1 to 10% by weight, preferably 2 to 10% by weight, and a melt flow rate of 1 to 600 g / measured under a load of 2160 g at 190 ° C. Ethylene-unsaturated carboxylic acid copolymer (copolymer (A-1)) having 10 minutes, preferably 10 to 500 g / 10 minutes, and an unsaturated carboxylic acid content of 11 to 25% by weight, preferably 13 to 23 Ethylene-unsaturated carboxylic acid copolymer (copolymer (A-) having a% by weight and a melt flow rate of 1 to 600 g / 10 minutes, preferably 10 to 500 g / 10 minutes, measured under a load of 2160 g at 190 ° C. Consisting of ionomers of the mixture of 2)). The mixed polymer composition as the base polymer of the mixed ionomer, the copolymer (A-1) and (A-2) is (A-1) 5 to 80 parts by weight, preferably 10 to 70 parts by weight, (A-2) It is preferable to mix | blend 95-20 weight part, Preferably it is 90-30 weight part, and to manufacture.

The ethylene-unsaturated carboxylic acid copolymer as the base polymer of the potassium ionomer may contain, for example, 40% by weight or less of the other polar monomer described above. When the layer (X) is used as the surface layer, the excessive amount of the polar monomer in the copolymer adversely affects the slip resistance and the scratch resistance, so the polar monomer content of the copolymer should be 30% by weight or less, preferably Should be less than 15%.

Considering the desired processability, scratch resistance, or miscibility when other components are blended, the melt flow rate measured under a load of 190 ° C. and 2160 g is 0.1 to 100 g / 10 minutes, preferably Preference is given to using potassium ionomers which are 0.2-50 g / 10 min.

In the multilayer structure of the present invention, the potassium ionomer is used as one or intermediate layers of the surface layers. Such layer (X) may be potassium ionomer itself, but other thermoplastic polymers may be blended to such an extent that the antistatic property, slip resistance and scratch resistance of the structure are not significantly impaired. Such thermoplastic polymer can be selected from polymeric materials which can be used as the surface layer (Y) described later. It is preferable to use ethylene polymers selected from olefin polymers, in particular ethylene homopolymers, copolymers made of ethylene and α-olefins having 3 or more carbon atoms, copolymers made of ethylene and vinyl acetate or unsaturated carboxylic acid esters. As such an ethylene polymer, it is not necessarily a requirement to use a virgin product. For example, in the case of using an ethylene polymer for the surface layer, it is possible to recycle waste materials such as defective products which occur when plastic molding is performed or the remaining edges. The blending ratio of the thermoplastic polymer is 95% by weight or less, preferably 90% by weight or less, particularly preferably 60% by weight or less based on the total amount of the potassium ionomer layer (X). In other words, it is desired that the potassium ionomer occupy at least 5% by weight, preferably at least 10% by weight, particularly preferably at least 40% by weight of the entire potassium ionomer layer (X).

In the potassium ionomer layer (X), in order to improve antistatic property, a polyhydroxy compound having two or more alcoholic hydroxyl groups can be blended. Specific examples thereof include polyoxyalkylene glycols of various molecular weights, such as polyethylene glycol, polypropylene glycol, and polyoxyethylene-polyoxypropylene glycol; And polyhydric alcohols such as glycerin, hexanetriol, pentaerythritol, and sorbitol, and ethylene oxide adducts thereof, and adducts of polyhydric amines and alkylene oxides.

The effective blending ratio of the polyhydroxy compound is in a range which does not impair the mechanical properties of the layer (X), for example, 15 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less, most preferably Preferably less than 0.1% by weight.

In the multilayer structure of the present invention, one surface layer (Y) is used for a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more (excluding the same resin or resin composition as that of layer (X)). In the present invention, the surface resistivity of the polymer material is measured in an atmosphere of 23 ° C. and 50% relative humidity.

In the present invention, the polymer material of the layer (Y) is a material in which the molded article exhibits a surface resistivity of 1 × 10 ¹⁴ Ω or more when molded alone. Examples of such polymeric materials are homopolymers of ethylene or copolymers of ethylene and α-olefins having 3 to 12 carbon atoms, for example high pressure polyethylene, medium or high density polyethylene, linear low density polyethylene, especially density 940 kg / linear low density polyethylene up to m ³ , and ultra low density polyethylene; Polypropylene; Poly-1-butene; Poly-4-methyl-1-pentene; Copolymers of ethylene and polar monomers such as ethylene-vinyl acetate copolymers; Copolymers of ethylene and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, monoethyl maleate, maleic anhydride and the like; Or ionomers such as Na, Li, Zn, Mg or Ca; Copolymers of ethylene with carbon monoxide and optionally unsaturated carboxylic acid esters or vinyl acetate; Polyolefin elastomers; Olefin polymers, such as

Styrene-based polymers such as polystyrene, high impact polystyrene or rubber-reinforced styrene-based resins such as ABS resins;

Polyesters such as polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, cyclohexanedimethanol copolymerized polyethylene terephthalate, polyester elastomers;

Polycarbonate;

Polymethyl methacrylate,

Or these 2 or more types of mixtures can be illustrated.

Among these polymer materials, an olefin polymer having excellent sealing properties, in particular, an ethylene homopolymer, a copolymer made of ethylene and an α-olefin having 3 or more carbon atoms such as linear low density polyethylene, a copolymer made of ethylene and a polar monomer, and the like are used. It is preferable. In particular, when using a material selected from ethylene-based polymers prepared using zinc ionomers and metallocene catalysts, the multilayer structure using such a material has excellent heat sealing properties and a polyhydroxy compound in the layer (X). Since the surface layer Y will have the outstanding antifouling property even if it is not added, it is preferable.

The zinc ionomer is obtained by partially neutralizing the ethylene-unsaturated carboxylic acid copolymer with zinc ions. At this time, other polar monomers may be optionally copolymerized, and other metal ions may coexist with zinc.

Here, as unsaturated carboxylic acid, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, monomethyl maleate, monoethyl maleate, etc. can be illustrated, A double acrylic acid or methacrylic acid is especially preferable. In addition, other polar monomers which may be copolymerized components include vinyl esters such as vinyl acetate and vinyl propionate; Unsaturated carboxylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-hexyl acrylate, isooctyl acrylate, methyl methacrylate, dimethyl maleate and diethyl maleate; Carbon monoxide etc. can be illustrated. In particular, unsaturated carboxylic esters are suitable as copolymerization components.

As the ethylene-unsaturated carboxylic acid copolymer used as the base polymer of the zinc ionomer, those having an unsaturated carboxylic acid content of about 1 to 25% by weight, especially about 5 to 20% by weight are preferable, and the polar monomer to be optionally copolymerized is For example, it may contain 40 weight% or less, Preferably it may contain 30 weight% or less. As zinc ionomer, the thing of neutralization degree 10 to 90%, especially about 15 to 80% is preferable. In consideration of the desired workability and practical properties, it is preferable to use a melt flow rate of 0.1 to 100 g / 10 minutes, especially 0.2 to 50 g / 10 minutes, measured under a load of 2160 g at 190 ° C.

Ethylene-based polymers prepared in the presence of a metallocene catalyst, which are suitably used as the polymer material of the surface layer (Y), copolymerize a homopolymer of ethylene or ethylene with an α-olefin having 3 or more carbon atoms, preferably 3 to 12 carbon atoms. As a copolymer obtained by using a catalyst component consisting of a transition metal of the periodic table IVV group, preferably a zirconium compound, and an organoaluminum-oxy compound catalyst component having at least one or more ligands having a cyclopentadienyl skeleton, and Thus, the polymer is prepared by polymerizing or copolymerizing ethylene in the presence of a catalyst formed of various additive components.

Examples of the α-olefin having 3 or more carbon atoms in the ethylene copolymer include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and the like. Can be illustrated. In particular, a copolymer with an α-olefin having about 3 to 12 carbon atoms is preferably used.

As the polymer or copolymer of ethylene produced in the presence of a metallocene catalyst, materials of various densities may be used depending on the α-olefin content of the copolymer, but the density is generally about 870 to 970 kg / m ³ , In particular, it is preferable to use 890-950 kg / m <^3> , especially the ethylene copolymer of 900-940 kg / m <^3> . In consideration of the desired workability and practical properties, it is preferable to use a melt flow rate of 0.1 to 100 g / 10 minutes, particularly 0.2 to 50 g / 10 minutes, measured under a load of 2160 g at 190 ° C.

The multilayer structure of the present invention comprises a potassium ionomer layer (X) and at least two layers comprising a layer (Y) of a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more. This structure may be composed of two layers, a layer (X) and a layer (Y), each of which forms a surface layer. In this case, however, another thermoplastic polymer layer or an adhesive layer may be provided between the two surface layers. The multilayer structure of the present invention may be composed of three or more layers including a layer (Y) constituting one surface layer and a layer (X) constituting an intermediate layer. In this case, the surface layer Z other than the layer Y may be a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more equivalent to that of the layer Y (excluding a resin or a resin composition such as that of the layer X). . Also in this case, another thermoplastic polymer layer or adhesive layer may be provided between the layer (Y) and the layer (X) or between the layer (X) and the layer (Z). Examples of the polymer material of the layer (Y) can be given as examples of the thermoplastic polymer layer. This layer may be a layer of recycled resin produced from recovered defective products, leftover edges, and the like, produced during the production of the multilayer structure. The material of such a regenerative resin layer is basically the same as the polymer material of any of the both surface layers, the intermediate layer, or a mixture of both, so that the miscibility with at least one of the surface layer or the intermediate layer is excellent, thereby promoting the interlayer adhesion. It is expected to contribute.

What can be used as an adhesive layer for the said objective may be what kind of thing, as long as it improves the interlayer adhesive strength. You may select from the thermoplastic polymers which were already illustrated as a raw material of a surface layer, or a hot melt adhesive or a coating adhesive may be sufficient. It is preferable to use an extrusion coating adhesive which is industrially selected from a thermoplastic or a composition in which a tackifier is added to the thermoplastic polymer.

One preferred aspect of the present invention is a three-layer structure consisting of a layer (X), an intermediate layer, and a layer (Y), wherein (a) the first surface layer (X) is a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer. And (b) the intermediate layer is a mixture consisting of 100 parts by weight of a linear low density polyethylene layer or 100 parts by weight of linear low density polyethylene and 100 parts by weight of potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer, preferably 50 parts by weight or less. (C) The other surface layer (Y) consists of a linear low density polyethylene layer. Linear low density polyethylenes typically have a density of 940 kg / m ³ or less. In particular, ethylene-based polymers produced by metallocene catalysts are preferred as polymer materials for the intermediate layer and other surface layers. The thickness ratio of the above-mentioned layers is preferably 10 to 90 of the first surface layer (X), 0 to 60 of the intermediate layer, and 10 to 90 of the other surface layer (Y).

Another preferred embodiment of the present invention is a three-layer structure consisting of an outer layer (X), an intermediate layer and an inner layer (Y), wherein the outer layer (X) is a layer made of potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer ( Non-foamed layer or foamed layer); The intermediate layer is a layer composed of an ethylene-unsaturated ester copolymer such as an ethylene-vinyl acetate copolymer; The inner layer (Y) is a layer made of ethylene homopolymer such as low density polyethylene, medium density polyethylene, high density polyethylene, metallocene type ethylene polymer, copolymer of ethylene and α-olefin, or the like. The multilayer bottles (containers) produced by the blow molding method from this multilayer structure have low surface reflection gloss that impart not only excellent antifouling property, slip resistance, scratch resistance, but also excellent visual quality to the resulting bottle, And an appearance such as a hazy silk fabriic.

Another preferred embodiment of the present invention is a three-layer structure consisting of an outer layer (Y), an intermediate layer (X), an inner layer (Z) or an outer layer (Z), an intermediate layer (X), and an inner layer (Y), wherein the outer layer ( Y) and inner layer (Z) (or outer layer (Z) and inner layer (Y)) consist of polyethylene such as low density polyethylene, medium density polyethylene, high density polyethylene, etc., or ethylene-unsaturated ester copolymer such as ethylene-vinyl acetate copolymer, , Intermediate layer (X) is a layer made of potassium ionomer of ethylene-unsaturated carboxylic acid copolymer. The multi-layer blow molded bottle (container) manufactured by the blow molding method from this multilayer structure is excellent in antifouling property, slip resistance, scratch resistance, and the like.

The multilayer structure of the present invention can be produced by extrusion coating, co-extrusion or blow molding. Although the total layer thickness of a multilayer structure is arbitrarily determined, it is good to make it into thickness of 10-3,000 micrometers, especially about 20-1,000 micrometers, for example. In the multilayer structure of the present invention, the 10% charge decay time (time to attenuate to 500V) at 20 ° C. at an applied voltage of +5000 V measured by at least one surface layer in an atmosphere of 23 ° C. and 50% relative humidity is 20 seconds. Hereinafter, Preferably it is 10 second or less, More preferably, it is 1 second or less. In the case where the layers X and Y each constitute the surface layer, only the layer X has the above charge decay characteristics, and the charge decay time of the layer Y may exceed 20 seconds. However, also in this case, the layer Y also preferably has a charge decay time of 20 seconds or less, preferably 10 seconds or less, more preferably 1 second or less. In order to obtain the above value, the thickness of the potassium ionomer layer (X) is 5 µm or more, preferably 10 µm or more, and when the surface layer (Y) or the reclaimed resin layer or the adhesive layer is provided on the surface layer (Y) It is preferable that the thickness of the bonded layer is 500 μm or less, especially 300 μm or less. In the case where layer (X) is an intermediate layer and layer (Z) is another surface layer, the charge decay time of layer (Z) may exceed 20 seconds as long as the charge decay time of layer (Y) is 20 seconds or less. Nevertheless, the charge decay time of the layer Z is also preferably 20 seconds or less, preferably 10 seconds or less, more preferably 1 second or less. In order to obtain the above value, when the surface layer (Z) or the recycled resin layer or the adhesive layer is provided, the total thickness of the surface layer (Z) and the recycled resin layer or the adhesive layer is preferably 500 µm or less, particularly 300 µm or less. Considering the practical performance, the thickness ratio of the total thickness of the other layers to the thickness of the potassium ionomer layer is preferably in the range of 0.1 to 100, in particular 0.5 to 50.

Various additives necessary can be mix | blended with each layer of the multilayer structure of this invention. Examples of such additives include antioxidants, light stabilizers, ultraviolet absorbers, pigments, dyes, lubricants, antiblocking agents, inorganic fillers, foaming agents, foaming accelerators, and the like. In particular, in the case of a multilayer bottle in which the outer layer is the layer X, when the foaming agent is mixed with the layer X, the foam becomes a bottle of excellent visual quality having a silky appearance. Such a multilayer bottle may contain 0.1 to 10 parts by weight of an organic or inorganic chemical foaming agent such as azodicarbonamide, dinitrosopentamethylenediamine, sulfonylhydrazide, sodium bicarbonate, and ammonium bicarbonate, per 100 parts by weight of the potassium ionomer. It can be obtained by blending to a degree and then foaming during blow molding.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples at all. In addition, in the following examples and comparative examples, the evaluation method of the performance of the used raw material and the multilayered structure obtained is shown below.

1. used as raw material

[Polymer material]

The polymer material shown in Table 1 was used.

[Potassium Ionomer]

The potassium ionomer of Table 3 which uses the base polymer of Table 2 as a raw material was used.

TABLE 1

 Abbreviation  Polymer material manufacturer  Trade name MFR * g / 10 min Density kg / m ³ Surface resistivity  Remarks MPE-1 Metallocene LLDPE MCI Evolue SP1540 4.0 915 10 ¹⁴ < MPE-2 Metallocene LLDPE MCI Evolue SP2040 4.0 920 10 ¹⁴ < PE-1 LDPE MCI Mirason M401 1.6 923 6 × 10 ¹⁵ PE-2 HDPE MCI Hi-zex 6200B 0.36 956 6 × 10 ¹⁵ PE-3 LDPE MCI Mirason 16 3.7 923 6 × 10 ¹⁵  EVA-1 Ethylene-Vinyl Acetate Copolymer  MDP  Evaflex P1905  2.5  940 2 × 10 ¹⁵ VA content 19 wt%  EVA-2 Ethylene-Vinyl Acetate Copolymer  MDP  Evaflex P1403  1.3  930 6 × 10 ¹⁵ VA content 14 wt%  EVA-3 Ethylene-Vinyl Acetate Copolymer  MDP  Evaflex EV5274  0.8  940 2 × 10 ¹⁵ VA content 17 wt%  EVA-4 Ethylene-Vinyl Acetate Copolymer  MDP  Evaflex EV250  15  950 9 × 10 ¹³ VA content 28 wt%  HM-1 Ethylene-Methacrylic Acid Copolymer Ionomer  MDP  Himilan 1554  1.0  940 2 × 10 ¹⁷  Zinc salt  HM-2 Ethylene-Methacrylic Acid Copolymer Ionomer  MDP  Himilan 1706  0.7  970 2 × 10 ¹⁷  Zinc salt

LLDPE: Linear Low Density Polyethylene

LDPE: Low Density Polyethylene

HDPE: High Density Polyethylene

VA: vinyl acetate

MCI: Mitsui Chemicals, Inc.

MDP: DU PONT-MITSUI POLYCHEMICALS CO., LTD.

*: Melt flow rate under load of 190 ° C., 2160 g

TABLE 2

 Abbreviation  Base polymer  Methacrylic acid content wt%  Isobutyl acrylate content wt% MFR * g / 10 min EMAA-1 Ethylene-Methacrylic Acid Copolymer 15 0 60 EMAA-2 Ethylene-Methacrylic Acid Copolymer 10 0 100 EMAA-3 Ethylene-Methacrylic Acid Copolymer 17.5 0 60  EMAAIBA Ethylene-Methacrylic Acid-Isobutyl Acrylate Copolymer  5  10  33

*: Melt flow rate under load of 190 ° C., 2160 g

TABLE 3

 Abbreviation Characteristics of Base Polymers Characteristics of K-Ionomer Added polyhydroxy compound wt% Composition (weight) Average acid content wt% Average MFR ^* g / 10 min Neutralization% MFR ^* g / 10 min KIO-1 Combination of EMAA-1 (50) and EMAA-2 (50)  12.5  78  92  5.0 PEG600 10 KIO-2 Combination of EMAA-3 (50) and EMAAIBA (50)  11.3  45  80  0.6  0 KIO-3 Combination of EMAA-1 (50) and EMAA-2 (50)  12.5  78  92  0.2  0 KIO-4 Combination of EMAA-1 (50) and EMAA-2 (50)  12.5  78  80  5.5 Glycerin 9 KIO-5 Combination of EMAA-3 (50) and EMAAIBA (50)  11.3  45  80  0.6 Glycerin 0.5

PEG600: polyethylene glycol (MW: 600)

*: Melt flow rate under load of 190 ° C., 2160 g

2. Property test method

(1) Antistatic performance

(1-1) decay time

After leaving the sample film at 23 ° C. and 50% relative humidity for 24 hours, using a Static Decay Meter Model 4060 manufactured by ETS, the time to decay from +5000 V to +500 V is applied as a 10% decay time. The decay time from voltage +5000 V to +2500 V was measured as 50% decay time.

(1-2) ash adhesion test method

Immediately after rubbing a sample film left at 23 ° C. and 50% relative humidity for 24 hours with a cotton cloth 10 times, ash of one cigarette was placed thereon and the sample film was turned over. Reattachment was judged as ash remained.

◎: ash is not left at all

○: some ash remaining

△: ash remains sparsely

×: ash remains almost entirely

(1-3) potential measurement

The multilayer container was left to stand in 40 degreeC and 80% relative humidity atmosphere for 24 hours, and the electric potential of the surface was measured with the static electricity measuring device (model SV-511, the product made by Static Co., Ltd.).

(1-4) Attachment of shavings of dried bonito

The multilayer container was left to stand in 40 degreeC and 80% relative humidity atmosphere for 24 hours, and the surface was rubbed 10 times with cotton cloth, and the bonito bag approached the container, and the adhesion state was observed.

○: not attached at all

△: somewhat attached

×: attached immediately

(2) slip

(2-1) Friction Coefficient (inclination angle method)

The sample film or cardboard to be measured was placed on the substrate surface. The same sample film was fixed at the bottom of the load to make contact with the substrate and the substrate was tilted. The coefficient of friction was calculated from the angle at which the load began to slip.

(3) scratch resistance

(3-1) reciprocating sliding abrasion

Cotton canvas No. Using a sheet of 10, the surface of the laminate was scratched under the conditions of a load of 430 g, a contact area of 224 m ² , a reciprocating speed of 60 times / minute, and a reciprocating number of times of 100 times, and the ratio of the cut surface area was micrograph (35 times, 2mm Measured in width).

◎: less than 5% of shaved area

○: area cut is more than 5% and less than 25%

(Triangle | delta): The shaved area is 25% or more and less than 50%.

×: area cut is 50% or more

Example 1

The thickness of each layer, using a multilayer cast film molding machine, having a first layer (surface layer) made of MPE-2, a second layer made of KI0-2 (intermediate layer), and a third layer made of MPE-2 (surface layer). The multilayer film as described in Table 4 was created. The ratio (layer thickness ratio) of the thickness of the first layer to the second layer of this multilayer structure was 0.75. Table 4 shows the evaluation results of the surface of the first layer of the obtained multilayer film.

Example 2

Made between Mitsui Kagaku Co., Ltd. as an adhesive layer between the first layer made of MPE-2 and the second layer made of KI0-2, and the second layer made of KI0-2 and the third layer made of MPE-2. Using the Admer (brand name) NF528 (MFR 2.2 g / 10min) which is an adhesive polyolefin, the multilayer film was created by the method similar to Example 1 except having changed the thickness ratio of each layer as shown in Table 4. . Table 4 shows the evaluation results of the thickness ratio of the sum of the first layer thickness and the upper adhesive layer thickness to the second layer thickness, and the antistatic performance of the first layer surface.

Example 3

The multilayer film was created by the method similar to Example 2 except having changed the 1st layer and the 3rd layer from MPE-2 to MPE-1, and changing the thickness of each layer as shown in Table 4. Table 4 shows the evaluation results of the layer thickness ratio and the antistatic performance of the first layer surface.

[Examples 4 to 5]

HM-1 was used as the first layer, melt blend (weight ratio 80/20) of EVA-1 and KI0-1 as the second layer, and EVA-2 as the third layer. Except having changed as described in, the multilayer film was created by the method similar to Example 1. Table 4 shows the evaluation results of the layer thickness ratio and the antistatic performance of the first layer surface.

Comparative Example 1

The single-layer film (50 micrometers in thickness) of MPE-2 was created by changing each layer to MPE-2 using the multilayer cast film molding machine. As shown in Table 4, the antistatic performance of the surface of the obtained single layer film was inadequate.

Comparative Example 2

The multilayer film was created by the method similar to Example 3 except having changed the 2nd layer from KI0-2 to HM-2. The antistatic performance of the surface of the first layer of the obtained multilayer film was insufficient at all, as shown in Table 4.

TABLE 4

Example Comparative example One 2 3 4 5 One 2    Composition and thickness of multilayer film (㎛)  First floor MPE-2 (15) MPE-2 (10) MPE-1 (20) HM-1 (50) HM-1 (200) MPE-2 (50) MPE-1 (20)  Adhesive layer  - NF528 (5) NF528 (20)  -  -  - NF528 (20)  2nd layer KIO-2 (20) KIO-2 (20) KIO-2 (40) EVA-1 + KIO-1 (40) EVA-1 + KIO-1 (40)  - HM-2 (40)  Adhesive layer  - NF528 (5) NF528 (20)  -  -  - NF528 (20)  3rd floor MPE-2 (15) MPE-2 (10) MPE-1 (20) EVA-2 (40) EVA-2 (40)  - MPE-1 (20) Layer thickness ratio ⁽¹⁾ 0.75 0.75 1.0 1.25 5.0 - 1.0  Evaluation of the surface of the first layer 10% charge decay time (sec)  0.01  10  0.79  0.02  0.02  60 <  60 < 50% charge decay time (sec)  -  0.01  0.04  0.01  -  -  - Tobacco ash test ◎ ◎ ○ ◎ ○ × ×

(1) Layer thickness ratio: (first layer + top adhesive layer) / second layer

[Examples 6 to 10 and Comparative Example 3]

Using a blow molding machine, the three-layer container which is 0.5 mm in thickness of each layer, and 100 ml of inner volume was produced by the laminated constitution as shown in Table 5. The evaluation result of the outer layer surface of this container is shown in Table 5 together.

TABLE 5

Example Comparative example 6 7 8 9 10 3  Floor composition Outer layer EVA-3 PE-1 EVA-3 PE-2 PE-2 PE-1  Mezzanine  KIO-2  KIO-2 Combination of KIO-2 (70) and PE-1 (30) ^* Combination of KIO-3 (70) and PE-2 (30) ^* Combination of KIO-4 (20) and PE-2 (80) ^*  PE-1 Inner layer PE-1 PE-1 PE-1 PE-2 PE-2 PE-1  Evaluation of the outer layer surface Voltage (kV) One 12 3 11 10 18 10% charge decay time (sec)  0.03  15  0.27  11  3 No attenuation 50% charge decay time (sec)  0.01  0.15  0.04  0.12  0.07 Inmeasurement Bonito bag adhesion test  ○  △  ○  △  ○  ×

*: Mixing ratio (by weight)

Example 11

Admer (brand name) NF528, which is an adhesive polyolefin made by Mitsui Kagaku Co., Ltd., a first layer (surface layer) made of KIO-2, a second layer (surface layer) made of MPE-1, and a multilayer cast film molding machine. The multilayer film which has the adhesive bond layer which consists of (MFR 2.2g / 10min) was created. The structure and thickness of each layer are as shown in Table 6. The ratio (layer thickness ratio) of the sum of the second layer thickness and the adhesive layer thickness to the first layer thickness of the multilayer structure was 1.5. Table 6 shows the evaluation results of the first layer surface and the second layer surface of the obtained multilayer film.

Example 12

A multilayer film was created in the same manner as in Example 11 except that KIO-2 in the first layer was changed to KIO-5. Table 6 shows the evaluation results of the layer thickness ratio of the obtained multilayer film and the antistatic performance of the first layer surface and the second layer surface of the film.

Example 13

The multilayer film was created by the method similar to Example 11 except having changed MPE-1 of 2nd layer into EVA-2, and changing the thickness of each layer as shown in Table 6 without an adhesive layer. Table 6 shows the evaluation results of the layer thickness ratio of the obtained multilayer film and the antistatic performance of the first layer surface and the second layer surface of the film.

[Comparative Example 4]

The multilayer film was created by the method similar to Example 11 except having changed KIO-2 of the 1st layer into HM-2, and changing the thickness of each layer as shown in Table 6. The evaluation result of the antistatic performance of the 1st layer surface and the 2nd layer surface of the obtained multilayer film, and the friction coefficient of the 1st layer surface were inadequate as shown in Table 6.

[Comparative Example 5]

By changing each layer to MPE-1, the single | mono layer film (40 micrometers in thickness) of MPE-1 was created. Antistatic performance, coefficient of friction and wear resistance were not sufficient at all, as shown in Table 6.

TABLE 6

Example Comparative example 11 12 13 4 5 Composition and thickness of multilayer film (㎛) First floor KIO-2 (40) KIO-5 (40) KIO-2 (50) HM-2 (40) MPE-1 (40) Adhesive layer NF528 (20) NF528 (20) - NF528 (20) - 2nd layer MPE-1 (40) MPE-1 (40) EVA-2 (50) MPE-1 (40) - Layer thickness ratio ⁽¹⁾ 1.5 1.5 1.0 1.5 -  Evaluation of the surface of the first layer 10% charge decay time (sec) 0.01 0.01 0.01 - 60 < 50% charge decay time (sec) 0.01 - - 60 < - Tobacco ash test ◎ ◎ ◎ × × Sliding friction coefficient Between films 0.53 0.60 0.53 2.4 < 2.4 < For carton 0.51 0.55 0.51 0.85 0.87 Reciprocating slip wear △ △ △ ◎ ×  Evaluation of the surface of the second layer 10% charge decay time (sec) 0.43 0.01 0.01 - 60 < 50% charge decay time (sec) 0.01 - - 60 < - Tobacco ash test ◎ ◎ ◎ × ×

(1) Layer thickness ratio: (second layer + adhesive layer) / first layer

Example 14

Using a blow molding machine, the three-layer container of each layer thickness of 0.5 mm and a volume of 100 ml was created by the laminated constitution as shown in Table 7. The surface reflection gloss (according to JIS z8741) of this multilayer container was 0.5%, haze (according to JIS K6714) was 65%, and flexural modulus (according to JIS K7106) was 147 MPa. Table 7 shows the evaluation results of the antistatic performance.

Examples 15 to 17 and Comparative Example 6

A three-layer container was created in the same manner as in Example 14 except that the layer structure was as described in Table 7. Table 7 shows the evaluation results of the antistatic performance.

TABLE 7

Example Comparative example 14 15 16 17 6  Floor composition  Outer layer  KIO-2 Combination of KIO-3 (80) and PE-2 (20) ^*  PE-2 Combination of KIO-4 (20) and PE-2 (80) ^*  PE-3 Mezzanine EVA-4 PE-2 PE-2 PE-2 PE-3  Inner layer  PE-3  PE-2 Combination of KIO-3 (90) and PE-2 (10) ^*  PE-2  PE-3  Evaluation of the outer layer surface Voltage (kV) One 3 2 0 18 Bonito bag adhesion test  ○  ○  ○  ○  ×

*: Mixing ratio (by weight)

According to the present invention, it is possible to provide a multilayer structure excellent in charge attenuation characteristics and excellent in antifouling property which can prevent adhesion of dust and powders due to static charge build-up. In addition, it is possible to provide a multilayer structure having excellent slip resistance and scratch resistance. Such structures can be used for various purposes, for example, in the form of films, tapes, sheets, tubes, pipes, bags, multilayer containers (such as blow molded containers), rods, injection molded articles, blow molded articles, and the like. Can be. This material is particularly preferably used as a packaging material. The potassium ionomer layer (X) as an outer layer as such a bag or a multilayer container is excellent in slip resistance, scratch resistance and antifouling property of the outer surface, and at the same time, heat sealing and antistatic property of the inner surface thereof. It can be used as an excellent, good packaging material. Moreover, the bottle made by making potassium ionomer layer (X) into an outer layer as such a multilayer container exhibits the outstanding slip resistance, scratch resistance, and antifouling property on the outer surface, and the visual high quality of a bottle. Thanks to its low surface reflectance luster, high haze and silky appearance that contribute to its creation, it has an outstanding appearance. The bag or multilayer container having the potassium ionomer layer (X) as an inner surface is a packaging material having an inner surface excellent in slipping and heat sealing properties, in addition to the antifouling property of the outer surface thereof, to protect the packaged material from damage. Can be used. In addition, molded articles having a potassium ionomer layer (X) as an intermediate layer and a layer (Y) having charge attenuation characteristics as described above on the outer surface thereof have antifouling properties, and dust can be accumulated on the surface. I knew. When the surface layer Y having the above-mentioned charge attenuation characteristics is used as the inner surface material as the packaging material of the powder, there is no electrostatic adhesion to the packaging of the powder and the commercial value of the product is maintained. Moreover, the outer surface of the multilayer blow container comprised from the multilayer structure of this invention which makes a potassium ionomer layer an intermediate | middle layer is excellent in sliding property, scratch resistance, and antifouling property.

The multilayer structure of this invention can be used for the following uses other than a packaging material. That is, the adhesive tape or film for semiconductors, such as a base material of a dicing tape and a back grinding film; Electrical and electronic materials such as marking films, IC carrier tapes, and electronic component tapings; Food packaging materials; Sanitary materials; Surface protective films (eg, glass, plastic or metallic plates, guard films or tapes for lenses); Steel wire cladding, clean room curtains, wallpaper, mats, flooring, lining of flexible containers, containers, shoes, battery separators, moisture vapor films, antifouling films , Dustproof film, PVC replacement film; It can be used for various cosmetics, detergents, shampoos, rinses and the like tubes and bottles.

The multilayer structure of the present invention can be used by providing an adhesive layer on one or both surfaces of the surface layer. As such an adhesive layer, rubber type, acryl type, silicone type, etc. are mentioned. The multilayer structure of the present invention may be, for example, a base such as a biaxially oriented film or sheet such as polyethylene terephthalate, polyamide or polypropylene, or a styrene resin such as acrylic resin, polycarbonate, ABS resin or polystyrene, polyacetal or the like. It can be used in the form of laminated on the item (item) containing the plate-shaped molded article of. When used as such an antifouling surface material, the multilayer structure of the present invention is laminated with the layer (Y), the layer (X), or the layer (Z) in contact with the substrate face-to-face, or an adhesive layer. Lamination can be used via. Examples of substrates that can be used in the application include foils of various plastics, papers, woods, metals, and the like, single layer or multilayer materials such as sheets, foams, fabrics, nonwovens, and the like.

Claims (34)

Layer (X) consisting of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of said potassium ionomer and a thermoplastic polymer, Layer (Y) comprising a polymer material having a surface resistivity of at least 1 × 10 ¹⁴ Ω or more consisting of at least one polymer selected from olefinic polymers, styrene-based polymers, polyesters, polycarbonates, and polymethylmethacrylates Consists of at least two layers comprising Wherein at least one surface layer has a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less. The method of claim 1, Multi-layer structure, wherein one of the surface layer is composed of the layer (Y). The method of claim 2, One of the surface layers consists of said layer (X) and the other surface layer consists of said layer (Y), The layer (X) has a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less, The layer (Y) has a multilayer structure having a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less. Layer (X) consisting of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of said potassium ionomer and a thermoplastic polymer, At least one of the surface layers comprising a polymer material having a surface resistivity of at least 1 × 10 ¹⁴ Ω or more consisting of at least one polymer selected from olefinic polymers, styrene-based polymers, polyesters, polycarbonates, and polymethylmethacrylates ( Y) Consists of at least two layers comprising The surface layer (Y) has a multilayer structure having a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less. The method of claim 4, wherein The other surface layer is a multilayer structure consisting of the layer (X). The method of claim 5, The other surface layer (X) has a multilayer structure having a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less. The method of claim 4, wherein The structure consists of three or more layers, The layer (X) is an intermediate layer, and the other surface layer (Z) is made of a polymer material having a surface resistivity of 1 × 10 ¹⁴ Ω or more. The method of claim 7, wherein The surface layer (Z) has a multi-layer structure having a 10% charge decay time at an applied voltage of +5000 V measured at 23 ° C. and 50% relative humidity of 20 seconds or less. The method according to any one of claims 1 to 8, The said potassium ionomer is a multilayer structure which consists of an ionomer whose neutralization degree by potassium ion is 60% or more of the ethylene-unsaturated carboxylic acid copolymer whose unsaturated carboxylic acid content is 10-30 weight%. The method of claim 9, The potassium ionomer is a mixed ionomer of two or more ethylene-unsaturated carboxylic acid copolymers having different unsaturated carboxylic acid contents, Wherein the average carboxylic acid content of the ethylene-unsaturated carboxylic acid copolymers is 10 to 20% by weight, and the difference between the highest acid content and the lowest acid content is 2 to 20% by weight. The method of claim 10, The potassium ionomer, Ethylene-unsaturated carboxylic acid copolymer (copolymer (A-1)) having an unsaturated carboxylic acid content of 1 to 10% by weight and a melt flow rate of 1 to 600 g / 10 minutes measured at a load of 2160 g at 190 ° C. )Wow, Ethylene-unsaturated carboxylic acid copolymer (copolymer (A-2)) having an unsaturated carboxylic acid content of 11 to 25 wt%, 190 ° C, and a melt flow rate of 1 to 600 g / 10 min, measured under a load of 2160 g. Consisting of, Of the mixed copolymer composition having an average unsaturated carboxylic acid content of 10 to 30% by weight and an average melt flow rate of 1 to 300 g / 10 min, measured under a load of 2160 g at 190 ° C, A multilayer structure that is a mixed ionomer having a degree of neutralization of at least 60%. The method of claim 11, The mixed copolymer composition is 5 to 80% by weight of the ethylene-unsaturated carboxylic acid copolymer (copolymer (A-1)) and 95 to 80% by weight of the ethylene-unsaturated carboxylic acid copolymer (copolymer (A-2)). Multi-layered structure produced at a blending ratio of 20% by weight. The method of claim 9, A multilayer structure wherein a polyhydroxy compound is blended into the layer (X) in a proportion of up to 15% by weight relative to the potassium ionomer. The method of claim 9, A multilayer structure wherein a polyhydroxy compound is blended into the layer (X) in a proportion of 0.1% by weight or less relative to the amount of the potassium ionomer. The method according to claim 1 or 4, The thermoplastic polymer in the layer (X) is an olefinic polymer. The method according to claim 1 or 4, The multilayer material of said layer (Y) is an olefinic polymer. The method of claim 16, The olefin-based polymer is a linear low density polyethylene or zinc ionomer multilayer structure. The method of claim 17, Wherein said linear low density polyethylene is a polymer or copolymer of ethylene, produced by a metallocene catalyst. The method of claim 7, wherein The multilayer material of the layer (Z) is an olefin polymer. The method of claim 19, The olefin-based polymer is a linear low density polyethylene or zinc ionomer multilayer structure. The method of claim 20, The linear low density polyethylene is a multi-layered structure of an ethylene-based copolymer prepared by a metallocene catalyst. The method of claim 4, wherein The multilayer structure (a) a layer consisting of potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer, (b) a layer consisting of a mixture of linear low density polyethylene or 100 parts by weight of linear low density polyethylene and 100 parts by weight of potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer, and (c) a layer consisting of linear low density polyethylene Multi-layer structure consisting of three layers of. The method of claim 7, wherein The multilayer structure, (a) a layer consisting of polyethylene or ethylene-unsaturated ester copolymers, (b) a layer consisting of a potassium ionomer of an ethylene-unsaturated carboxylic acid copolymer or a mixture of said potassium ionomer and a thermoplastic copolymer, and (c) a layer consisting of polyethylene or an ethylene-unsaturated ester copolymer Multi-layer structure consisting of three layers of. The method of claim 4, wherein A multilayer structure wherein an adhesive layer and / or a recycled resin layer is provided between the layer (X) and the layer (Y). The method according to claim 3 or 4, The multilayer structure, (a) a layer consisting of potassium ionomer of ethylene-unsaturated carboxylic acid copolymer, foamed or unfoamed, (b) a layer consisting of an ethylene-unsaturated ester copolymer, and (c) a layer consisting of polyethylene Multi-layer structure consisting of three layers of. The method of claim 7, wherein A multilayer structure wherein an adhesive layer and / or a recycled resin layer are provided between the layer (X) and the layer (Z). The method according to any one of claims 1 to 8, 19 to 24, or 26, Multi-layer structure, wherein the thickness ratio of the total thickness of the other layers to the layer (X) is in the range of 0.1 to 100. The sheet or film which consists of a multilayered structure in any one of Claims 1-8, 19-24, or 26. The method of claim 28, A sheet or film whose friction coefficient is 1.0 or less. The method of claim 28, Sheets or films used for packaging. A bag or multilayer container composed of the multilayer structure according to any one of claims 1 to 8, 19 to 24, or 26. The method of claim 31, wherein A multilayer container, wherein said container is produced by blow molding method. The method of claim 31, wherein Bag or multilayer container wherein layer (X) is used as innermost layer or outermost layer. Flooring consisting of the multilayer structure according to any one of claims 1 to 8, 19 to 24, or 26.