JP2022022262A - Laminate and packaging bag having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate at least having a substrate layer and a sealant layer in this order, having an excellent antistatic performance while improving a biomass degree.

SOLUTION: A laminate includes at least a substrate layer and a sealant layer in this order. The laminate has an antistatic performance. The sealant layer has a three-layer constitution including, from the substrate layer side, an inner layer, a middle layer and an outer layer. The middle layer of the sealant layer includes a linear low-density polyethylene derived from biomass. The sealant layer has the total thickness of 40 μm or more and 70 μm or less. The laminate is capable of producing a packaging bag having an excellent antistatic performance while improving a biomass degree.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a laminate including at least a base material layer and a three-layered sealant layer in this order. Further, the present invention relates to a packaging bag provided with the laminate.

In recent years, with the growing demand for the construction of a sound material-cycle society, it is desired to break away from fossil fuels in the material field as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by using it, it becomes carbon dioxide and water again, so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass materials is rapidly advancing, and attempts are being made to manufacture various resins from biomass raw materials.

As a resin derived from biomass, polylactic acid (PLA), which is produced via lactic acid fermentation, started commercial production in advance, but its biodegradable and other plastic performance is currently a general-purpose plastic. Because it is very different from the above, there are limits to the product applications and product manufacturing methods, and it has not been widely used. In addition, life cycle assessment (LCA) evaluation is being conducted for PLA, and discussions are being held on energy consumption during PLA manufacturing and equivalence when replacing general-purpose plastics.

Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester are used. In particular, polyethylene is molded into films, sheets, bottles and the like, and is used for various purposes such as packaging materials, and is widely used all over the world. Therefore, using polyethylene derived from conventional fossil fuels has a large environmental load. Therefore, it is desired to reduce the amount of fossil fuel used in the production of polyethylene by using a raw material derived from biomass. For example, to date, resin films for packaging products using biomass-derived polyethylene have been proposed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2012-251006

The present inventors have a biomass polyolefin made from biomass-derived ethylene as a raw material together with a polyolefin produced using ethylene obtained from a conventional fossil fuel (hereinafter, may be simply referred to as "fossil fuel-derived polyolefin"). By using (hereinafter, sometimes simply referred to as "biomass polyolefin"), we have developed a packaging bag with a high degree of biomass while keeping costs down. In the process, the present inventors face a technical problem that the performance as a packaged product may be impaired because the powder adheres around the packaging bag when the powdery contents are taken out. did. Therefore, as a result of further studies, the present inventors have found a layer structure of a laminated body capable of producing a packaging bag having excellent antistatic performance while improving the biomass degree, and have completed the present invention. rice field.

Therefore, an object of the present invention is to provide a laminate having excellent antistatic performance while improving the degree of biomass.

According to the first aspect of the present invention.
A laminate including at least a base material layer and a sealant layer in this order.
The laminate has antistatic performance and
The sealant layer has a three-layer structure of an inner layer, an intermediate layer, and an outer layer in order from the base material layer side.
The intermediate layer of the sealant layer contains a linear low density polyethylene derived from biomass and contains.
Provided is a laminate in which the thickness of the entire sealant layer is 40 μm or more and 70 μm or less.

In the first aspect of the present invention, it is preferable that the intermediate layer of the sealant layer further contains linear low-density polyethylene derived from fossil fuel.

In the first aspect of the present invention, it is preferable that the inner layer and the outer layer of the sealant layer contain linear low-density polyethylene derived from fossil fuel.

In the first aspect of the present invention, the biomass degree of the intermediate layer of the sealant layer is preferably 50% or more and 95% or less.

In the first aspect of the present invention, the biomass degree of the entire sealant layer is preferably 10% or more and 35% or less.

In the first aspect of the present invention, it is preferable that the base material layer contains an antistatic agent.

In the first aspect of the present invention, it is preferable that the laminate further includes a printing layer between the base material layer and the sealant layer.

In the first aspect of the present invention, it is preferable that the laminated body further includes an adhesive layer between the printed layer and the sealant layer.

In the second aspect of the present invention, a packaging bag provided with the laminate is provided.

The laminate according to the present invention includes at least a base material layer and a sealant layer having a three-layer structure of an inner layer, an intermediate layer, and an outer layer in this order, and the intermediate layer of the sealant layer is a linear low-density polyethylene derived from biomass. Since the laminate contains and has antistatic performance, it is possible to manufacture a packaging bag having excellent antistatic performance while improving the degree of biomass.

It is a schematic sectional drawing which shows an example of the laminated body by this invention. It is a schematic sectional drawing which shows an example of the laminated body by this invention. It is a schematic front view which shows an example of the standing pouch by this invention.

<Laminated body>
The laminate according to the present invention includes at least a base material layer and a sealant layer in this order, and the sealant layer has a three-layer structure of an inner layer, an intermediate layer, and an outer layer in order from the base material layer side, and has antistatic performance. It has. Since the laminated body has antistatic performance, the packaging bag manufactured by using the laminated body suppresses the powdery body from adhering around the packaging bag at the time of taking out even if the content is a powdery body. can do. The laminate may further include a printing layer, an adhesive layer, another layer, and the like. When the laminate includes two or more other layers, each may have the same composition or different compositions.

The laminated body according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminated body according to the present invention are shown in FIGS. 1 and 2.
The laminate 10 shown in FIG. 1 includes a base material layer 11 and a three-layered sealant layer 12 composed of an inner layer 13, an intermediate layer 14, and an outer layer 15 in this order. In the packaging bag provided with the laminate 10, the sealant layer 14 is located on the content side.
The laminate 20 shown in FIG. 2 includes a base material layer 21, a printing layer 26, an adhesive layer 27, and a three-layered sealant layer 22 composed of an inner layer 23, an intermediate layer 24, and an outer layer 25 in this order. It is a thing. In the packaging bag provided with the laminate 20, the sealant layer 24 is located on the content side.
Hereinafter, each layer constituting the laminated body will be described.

[Base layer]
The laminate according to the present invention includes a base material layer when manufacturing a packaging bag. By imparting antistatic performance to the base material layer, the packaging bag manufactured using the laminated body suppresses the powdery body from adhering around the packaging bag when the contents that are the powdery body are taken out. can do.

As a method of imparting antistatic performance to the base material layer, an antistatic agent may be contained in the base material layer. Antistatic agents are roughly classified into cationic antistatic agents, anionic antistatic agents, zwitterionic antistatic agents, and nonionic antistatic agents. Examples of the cationic antistatic agent include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts. Examples of the anionic antistatic agent include fatty acid salts, higher alcohol sulfate esters, liquid fatty oil sulfate esters, aliphatic amine and aliphatic amide sulfates, aliphatic alcohol phosphate ester salts, and dibasic fatty acid esters. Examples thereof include salts, fatty acid amide sulfonates, alkyl sulfonates, alkylaryl sulfonates, formalin-fused naphthalene sulfonates, and examples of the amphoteric ionic antistatic agent include imidazoline derivatives, ammonium carboxylates, and sulfuric acid. Examples thereof include ammonium ester, ammonium phosphate ester, ammonium sulfonate and the like. Among these, a sulfonic acid metal salt having an alkyl group having 8 to 20 carbon atoms is preferable because it has a good balance between effect and economy. Examples of the nonionic antistatic agent include ethylene oxide adducts of fatty alcohols, ethylene oxide adducts of fatty acids, and ethylene oxide adducts of alkylphenols. In addition to the above, waxes, paraffins, and silicone compounds can also be used. One or more of these antistatic agents can be used.

As the base material layer, for example, polyester such as polyethylene terephthalate, polyamide such as nylon, and polyolefin such as polypropylene can be used, and a polyethylene terephthalate film can be used from the viewpoint of moldability and durability as a packaged product. preferable. The polyethylene terephthalate used for the base material layer may be derived from biomass or fossil fuel. The substrate layer may contain both biomass-derived polyethylene terephthalate and fossil fuel-derived polyethylene terephthalate. By using polyethylene terephthalate derived from biomass for at least a part of the base material layer, the degree of biomass of the entire laminate can be improved. The biomass-derived polyethylene terephthalate is a polyethylene terephthalate in which ethylene glycol derived from biomass is used as a diol unit and terephthalic acid derived from fossil fuel is used as a dicarboxylic acid unit.

The method for producing the base material layer is not particularly limited, but it can be formed by using the resin composition containing the antistatic agent and, if necessary, a binder, and the resin composition is formed into a film to form a base film. It is preferable to do so. As one aspect of the method for producing a base film, an example in which the base film is a biaxially stretched polyethylene terephthalate film containing an antistatic agent will be described. A mixture of a polyethylene terephthalate resin and an alkyl sulfonic acid metal salt was melt-extruded at a resin temperature of 270 to 290 ° C. using an extruder equipped with a coat hanger type T-die, and the temperature was adjusted to 10 to 40 ° C. Wrap it in close contact with the cooling drum to cool it. Subsequently, the obtained unstretched sheet can be biaxially stretched at a temperature of 90 to 140 ° C. to obtain a base film.

The base material layer is preferably stretched, and more preferably biaxially stretched.
When the base material layer is a stretched polyethylene terephthalate film, the stretched polyethylene terephthalate film used for the base material layer has a tensile strength of 150 MPa or more and 300 MPa or less in the MD direction, more preferably 200 MPa or more and 300 MPa or less in the TD direction. It is preferably 150 MPa or more and 300 MPa or less, more preferably 150 MPa or more and 300 MPa or less, and the tensile elongation is preferably 50% or more and 250% or less, more preferably 70% or more and 200% or less in the MD direction, and TD. In the direction, it is preferably 50% or more and 250% or less, and more preferably 60% or more and 200% or less.
When the base material layer is a stretched nylon film, the stretched nylon film used for the base material layer has a tensile strength of preferably 150 MPa or more and 350 MPa or less in the MD direction, more preferably 200 MPa or more and 300 MPa or less, and preferably in the TD direction. It is 150 MPa or more and 400 MPa or less, more preferably 200 MPa or more and 350 MPa or less, and the tensile elongation is preferably 50% or more and 200% or less in the MD direction, more preferably 70% or more and 150% or less, and in the TD direction. It is preferably 30% or more and 200% or less, and more preferably 50% or more and 150% or less.
When the base material layer is a stretched polypropylene film, the stretched polypropylene film used for the base material layer has a tensile strength of preferably 50 MPa or more and 250 MPa or less in the MD direction, more preferably 70 MPa or more and 200 MPa or less, and preferably in the TD direction. It is 150 MPa or more and 450 MPa or less, more preferably 200 MPa or more and 400 MPa or less, and the tensile elongation is preferably 100% or more and 300% or less in the MD direction, more preferably 150% or more and 250% or less, and in the TD direction. It is preferably 20% or more and 100% or less, and more preferably 30% or more and 80% or less.
The above tensile strength and tensile elongation can be measured according to JIS K 7127.

The base material layer preferably has a thickness of 5 μm or more and 40 μm or less, and more preferably 8 μm or more and 25 μm or less. The thickness of the base material layer may be different or the same. When the thickness of the base material layer is about the above range, molding processing is easy and it can be suitably used as a packaging material.

[Antistatic layer]
Instead of imparting antistatic performance to the base material layer, an antistatic layer containing the antistatic agent may be separately provided on the base material layer. The antistatic layer will be located on the outermost layer when the packaging bag is manufactured. The antistatic layer is not particularly limited as long as it contains the above antistatic agent. The method for producing the antistatic layer is not particularly limited, but it can be formed by using the same resin composition as the base material layer, and it is preferable to form the resin composition to form an antistatic film.

[Sealant layer]
The laminate according to the present invention includes a sealant layer that is on the content side when the packaging bag is manufactured. The sealant layer has a three-layer structure of an inner layer, an intermediate layer, and an outer layer in order from the base material layer side.

The intermediate layer of the sealant layer contains a biomass-derived linear low-density polyethylene (LLDPE), and may further contain a fossil fuel-derived linear low-density polyethylene. Since the intermediate layer of the sealant layer contains linear low-density polyethylene derived from biomass, the degree of biomass of the laminate can be increased. In the intermediate layer of the sealant layer, the content of linear low-density polyethylene derived from biomass is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 90% by mass or less, and fossil fuel. The content of the derived linear low-density polyethylene is preferably 0% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less. When the content of the linear low-density polyethylene derived from biomass in the intermediate layer of the sealant layer is within the above range, the biomass degree of the entire laminate can be increased.

The inner and outer layers of the sealant layer preferably contain linear low-density polyethylene derived from a conventionally known fossil fuel in consideration of sealing properties, adhesion to the base material layer, manufacturing cost, and the like.

The biomass degree of the intermediate layer of the sealant layer is preferably 50% or more and 95% or less, and more preferably 60% or more and 90% or less. The biomass degree of the entire sealant layer is preferably 10% or more and 35% or less, and more preferably 15% by mass or more and 30% by mass or less. If the biomass level is within the above range, the amount of fossil fuel used can be reduced while the cost can be suppressed, and the environmental load can be reduced. In the present invention, the "biomass degree" indicates the weight ratio of the biomass-derived component.

The above-mentioned "biomass degree" (carbon concentration derived from biomass) is a value of C14 content obtained by a radiocarbon (C14) measuring method based on ASTM-D6866. Since carbon dioxide in the atmosphere contains C14 at a fixed ratio (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, the ratio of carbon derived from biomass can be calculated by measuring the ratio of C14 contained in all carbon atoms in the intermediate layer of the sealant layer. In the present invention, when the content of C14 in the intermediate layer of the sealant layer is PC14, the carbon content Pbio derived from biomass can be determined as follows.
Pbio (%) = PC14 / 105.5 × 100
Note that PMC is an abbreviation for Percent Modern Carbon.

Biomass polyethylene is a monomer polymer containing ethylene derived from biomass. Since ethylene derived from biomass is used as the monomer as a raw material, the polymerized polyolefin is derived from biomass. The content of biomass-derived ethylene in the raw material monomer does not have to be 100% by mass, and is, for example, preferably 50% or more, more preferably 80% or more. The raw material monomer may contain ethylene derived from fossil fuels, or may contain α-olefin monomers such as butylene, hexene, and octene. Even in such a case, the obtained polymer is called biomass polyethylene. By containing the α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear one.

For example, biomass-derived ethylene can be produced using biomass-derived ethanol as a raw material. In particular, it is preferable to use fermented ethanol derived from biomass obtained from plant raw materials. The plant material is not particularly limited, and conventionally known plants can be used. For example, corn, sugar cane, beets, and manioc can be mentioned.

In the present invention, the fermented ethanol derived from biomass refers to ethanol obtained by contacting a culture solution containing a carbon source obtained from a plant raw material with a microorganism producing ethanol or a product derived from a crushed product thereof, producing the product, and then purifying the ethanol. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to the purification of ethanol from the culture broth. For example, a method of adding benzene, cyclohexane or the like and azeotropically boiling, or removing water by membrane separation or the like can be mentioned.

Linear low-density polyethylene is obtained by polymerizing ethylene and a small amount of α-olefin by a low-pressure polymerization method (gas phase polymerization method using a Ziegler-Natta catalyst or liquid phase polymerization method using a metallocene catalyst). .. The linear low-density polyethylene has many short molecular chains in the molecular chain and has excellent sealing performance.

Linear low density polyethylene is less than 0.93 g / cm ³ , preferably 0.91 g / cm ³ or more and less than 0.93 g / cm ³ , more preferably 0.912 g / cm ³ or more and 0.928 g / cm ³ or less. More preferably, it has a density of 0.915 g / cm ³ or more and 0.925 g / cm ³ or less. The density of the linear low-density polyethylene is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1980. When the density of the linear low-density polyethylene is 0.91 g / cm ³ or more, the rigidity of the sealant layer containing the linear low-density polyethylene can be increased, and it can be suitably used as the inner layer of the packaging bag. Further, when the density of the linear low-density polyethylene is less than 0.93 g / cm ³ , the mechanical strength of the sealant layer can be increased, and it can be suitably used as the inner layer of the packaging bag.

The linear low-density polyethylene is 0.1 g / 10 minutes or more and 10 g / 10 minutes or less, preferably 0.2 g / 10 minutes or more and 9 g / 10 minutes or less, and more preferably 1 g / 10 minutes or more and 8.5 g / 10 minutes or less. It has the following melt flow rate (MFR). The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method specified in JIS K7210-1995. When the MFR of the linear low-density polyethylene is 0.1 g / 10 minutes or more, the extrusion load during the molding process can be reduced. Further, when the MFR of the linear low-density polyethylene is 10 g / 10 minutes or less, the mechanical strength of the sealant layer can be increased.

As the biomass polyethylene preferably used in the present invention, a linear low-density polyethylene derived from biomass manufactured by Brasschem Co., Ltd. (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 minutes) , Biomass degree 87%), Linear low density polyethylene derived from biomass manufactured by Brasschem (trade name: SLL318, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 minutes, biomass degree 87%), Examples thereof include linear low-density polyethylene derived from biomass manufactured by Brasschem (trade name: SLH218, density: 0.916 g / cm ³ , MFR: 2.3 g / 10 minutes, biomass degree 87%).

As the linear low-density polyethylene derived from biomass, for example, those using sugar cane as a raw material are produced. The dispersity of such linear low-density polyethylene derived from sugar cane can be 4 or more and 7 or less. On the other hand, the dispersity of the fossil-derived linear low-density polyethylene is usually 1.5 or more and 3.5 or less.

The thickness of the entire sealant layer is preferably 40 μm or more and 80 μm or less, and more preferably 45 μm or more and 70 μm or less. When the thickness of the sealant layer is within the above range, sufficient sealing suitability can be imparted when the packaging bag is manufactured. The thickness of the intermediate layer in the sealant layer is preferably 20% or more and 50% or less, and more preferably 30% or more and 40% or less with respect to the thickness of the entire sealant layer. Further, the thicknesses of the inner layer and the outer layer may be the same or different.

[Print layer]
The printing layer is used for decoration, display of contents, display of best-by date, display of manufacturers, sellers, etc., and for the purpose of giving a sense of beauty, such as letters, numbers, patterns, figures, symbols, and patterns. A layer that forms any desired print pattern. The printed layer can be provided as needed, and can be provided, for example, between the base material layer and the sealant layer. The printing layer may be provided on the entire surface of the base material layer, or may be provided on a part of the base material layer. The printed layer can be formed by using a conventionally known pigment or dye, and the forming method thereof is not particularly limited.

The printed layer preferably has a thickness of 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 5 μm or less, and further preferably 1 μm or more and 3 μm or less.

[Adhesive layer]
The adhesive layer is a layer provided when adhering any two layers, and can be provided, for example, between the print layer and the sealant layer.

When the two layers are bonded by the dry laminating method, the adhesive layer can be an adhesive layer formed by applying an adhesive to the surface of the layer on the side to be laminated and drying the adhesive layer. Examples of the adhesive include one-component or two-component curable or non-curable vinyl-based, (meth) acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, and others. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. As the two-component curable adhesive, a cured product of a polyol and an isocyanate compound can be used. As a coating method of the above-mentioned laminating adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fonten method, a transfer roll coating method, or other methods can be applied. ..

The adhesive layer may be an adhesive resin layer used when the two layers are bonded by the sand laminating method. The thermoplastic resin that can be used for the adhesive resin layer includes a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, or a copolymer resin containing these resins as a main component, a modified resin, or a mixture (including an alloy). ) Can be used. Examples of the polyolefin-based resin include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), linear (linear) low-density polyethylene (LLDPE), polypropylene (PP), and metallocene catalysts. Ethylene-α / olefin copolymer polymerized using, random or block copolymer of ethylene / polypropylene, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene / Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, and adhesion between layers. It is possible to use an acid-modified polyolefin-based resin obtained by modifying the above-mentioned polyolefin-based resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid. can. Further, as the polyolefin resin, an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, a resin obtained by graft-polymerizing or copolymerizing an ester monomer and the like can be used. These materials can be used alone or in combination of two or more. As the cyclic polyolefin resin, for example, a cyclic polyolefin such as an ethylene-propylene copolymer, polymethylpentene, polybutene, or polynorbonene can be used. These resins can be used alone or in combination of two or more. As the polyethylene-based resin described above, a resin using the above-mentioned ethylene derived from biomass as a monomer unit can be used to further improve the degree of biomass.

When laminating the adhesive resin layer by the melt-extruded laminating method, an anchor coat layer formed by applying an anchor coating agent and drying may be provided on the surface of the layer on the laminated side. Examples of the anchor coating agent include any resin having a heat resistant temperature of 135 ° C. or higher, for example, an anchor coating agent made of a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, polyethyleneimine, or the like. An anchor coating agent which is a cured product of a polyacrylic or polymethacrylic resin (polyester) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used in combination with this as an additive, or nitrocellulose may be used in combination to enhance heat resistance.

The laminated body may have one adhesive layer or may include two or more adhesive layers. For example, when two adhesive layers are included in the laminate, one adhesive layer may be referred to as an adhesive layer and the other adhesive layer may be referred to as a second adhesive layer.

The dried anchor coat layer has a thickness of 0.1 μm or more and 1 μm or less, preferably 0.3 μm or more and 0.5 μm or less. The dried adhesive layer has a thickness of 1 μm or more and 10 μm or less, preferably 2 μm or more and 5 μm or less. The adhesive resin layer preferably has a thickness of 5 μm or more and 50 μm or less, preferably 10 μm or more and 30 μm or less.

[Other layers]
The laminate according to the present invention may further include a thermoplastic resin layer or the like as another layer. As the thermoplastic resin layer, the same material as the adhesive resin layer can be used.

The laminate according to the present invention may be provided with a barrier layer as another layer. The barrier layer is provided to extend the shelf life of the contents, and is a vapor-deposited layer of a metal foil such as aluminum, a metal oxide such as aluminum, a metal oxide such as aluminum oxide, or an inorganic oxide such as silicon oxide, and ethylene. -A resin layer having a gas barrier property such as a vinyl alcohol copolymer (EVOH), a polyvinylidene chloride resin (PVDC), and an aromatic polyamide such as nylon MXD6 can be used. Further, on the vapor deposition layer, the general formula R1nM (OR2) m (however, in the formula, R1 and R2 represent organic groups having 1 to 8 carbon atoms, M represents a metal atom, and n represents 0 or more. Represents an integer of, m represents an integer of 1 or more, n + m represents the valence of M), at least one alkoxide, and a polyvinyl alcohol-based resin and / or as described above. A gas barrier coating film containing an ethylene / vinyl alcohol copolymer and further condensed by a solgel method in the presence of a solgel method catalyst, acid, water, and an organic solvent by a transparent gas barrier composition. May be provided.

<Manufacturing method of laminated body>
The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by using a conventionally known method such as a dry laminating method or a sand laminating method.

The laminate according to the present invention is provided with a chemical function, an electrical function, a magnetic function, a mechanical function, a friction / wear / lubrication function, an optical function, a thermal function, a surface function such as biocompatibility, and the like. It is also possible to perform secondary processing for the purpose. Examples of secondary processing include embossing, painting, bonding, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, etc.) Coating, etc.) and the like. Further, the laminated body according to the present invention may be subjected to laminating processing (dry laminating or extruded laminating), bag making processing, and other post-treatment processing to produce a molded product.

<Packaging bag>
The packaging bag according to the present invention includes the above-mentioned laminate. For example, the above laminated body is used and folded in half, or two laminated bodies are prepared, the surfaces of the sealants are opposed to each other and overlapped, and the peripheral end thereof is, for example, a side seal type. , Two-way seal type, three-way seal type, four-way seal type, envelope sticker seal type, gassho sticker seal type (pillow seal type), fold seal type, flat bottom seal type, square bottom seal type, gusset type, etc. Can be heat-sealed to produce various forms of packaging bags.

In the above, as the heat sealing method, for example, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

Since the packaging bag has excellent antistatic performance while exhibiting a high degree of biomass, it can be suitably used for sealing a powdery substance that may adhere around the packaging bag. Examples of the powdery contents include dried foods such as wheat flour, barley flour, rice flour, kataguri powder, and seasoning powder, powder detergents, pharmaceutical powders, metal powders, and the like.

The packaging bag according to the present invention will be described with reference to the drawings. FIG. 3 shows an example of a schematic front view of the pouch according to the present invention.
The pouch 30 shown in FIG. 3 is manufactured in a standing pouch format, and the sealant layers of the wall surface films (using the above laminated body) 31, 31'are arranged so as to face each other, and the wall surface films 31, 31' It is formed in a form having a gusset portion formed by folding the bottom film (which may be the same as or different from the wall film) 32 inward and inserting the bottom film folded portion 33 between the lower portions of the bottom film. The bottom is heat-sealed by the bottom seal portion 34 of the ship bottom shape including the portion to form the bottom. At this time, cutout portions 32a and 32b of a substantially semicircular bottom sheet may be provided near the lower ends on both sides of the mountain-folded bottom film 32 to form the bottom seal portion 34. Next, both side edge portions of the wall surface films 31 and 31'are heat-sealed with the side sealing portions 35a and 35b to form a body portion, and the upper end portion is left as a filling port for the contents. The upper seal portion 36 provided at the filling port at the upper end is filled with the contents from this portion and then heat-sealed by, for example, a degassing seal. A chuck tape 37 having a male chuck tape attached to one wall film and a female tape attached to the other wall film is provided below the upper sealing portion 36 to form a standing pouch with a chuck tape. good. Further, between the upper seal portion 36 and the chuck tape 37, a cut line 38 by printing and notches 39a and 39b may be provided at both ends thereof. In the above example, an example in which the standing pouch 30 is formed by using two wall films and one bottom film has been described, but the standing pouch is formed by using one film or two films. You may try to do it.

The chuck tape was heat-bonded to a first tape body having a male-shaped fitting portion of ridges heat-bonded to the inner surface of one wall surface film, and to the inner surface of the other wall surface film so as to face the first tape body. It is composed of a second tape body having a female fitting portion of a recess. When the outer layer of the sealant layer is made of polyethylene, it is preferable that the chuck tape is also made of polyethylene from the viewpoint of thermally adhering the chuck tape to the inner surface of the wall surface film (outer layer of the sealant layer). It is preferable to use linear low-density polyethylene, low-density polyethylene, medium-density polyethylene, and high-density polyethylene for the chuck tape. When linear low-density polyethylene is used for the outer layer of the sealant layer, the chuck tape is also linear. It is more preferable to use low-density polyethylene.

<Other aspects>
According to the third aspect of the present invention.
A laminate including at least a base material layer and a sealant layer in this order.
The laminate has antistatic performance and
The sealant layer has a three-layer structure of an inner layer, an intermediate layer, and an outer layer in order from the base material layer side.
A laminate is provided in which the intermediate layer of the sealant layer contains a linear low-density polyethylene derived from biomass.
In the third aspect of the present invention, it is preferable that the intermediate layer of the sealant layer further contains linear low-density polyethylene derived from fossil fuel.
In the third aspect of the present invention, it is preferable that the inner layer and the outer layer of the sealant layer contain linear low-density polyethylene derived from fossil fuel.
In the third aspect of the present invention, the biomass degree of the intermediate layer of the sealant layer is preferably 50% or more and 95% or less.
In the third aspect of the present invention, the biomass degree of the entire sealant layer is preferably 10% or more and 35% or less.
In the third aspect of the present invention, the thickness of the entire sealant layer is preferably 40 μm or more and 80 μm or less.
In the third aspect of the present invention, it is preferable that the base material layer contains an antistatic agent.
In the third aspect of the present invention, it is preferable that the laminate further includes a printing layer between the base material layer and the sealant layer.
In the third aspect of the present invention, it is preferable that the laminated body further includes an adhesive layer between the printed layer and the sealant layer.
In the fourth aspect of the present invention, a packaging bag provided with the laminate is provided.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Example 1]
<Manufacturing of laminated body 1>
An antistatic biaxially stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Unitika Ltd., Embret PTME) was prepared as a base material layer, and a printing layer was formed on one surface of the polyethylene terephthalate film by gravure printing. In addition, the inner layer is a resin of linear low-density polyethylene derived from fossil fuel (density: 0.918 g / cm ³ , MFR: 3.8 g / 10 minutes, degree of biomass: 0%), and the intermediate layer is directly derived from biomass. Linear low density polyethylene 80 parts by mass (LLDPE, manufactured by Brasschem, trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 minutes, biomass degree 87%) and linear chain derived from fossil fuel Mixed resin consisting of 20 parts by mass of low-density polyethylene (70% biomass) and linear low-density polyethylene derived from fossil fuel as an outer layer (density: 0.918 g / cm ³ , MFR: 3.8 g / 10 minutes, Three layers of resin with a biomass degree of 0% are extruded together and formed into a film by the inflation method, and a laminated polyethylene film derived from biomass (biomass degree 23%, thickness 50 μm, thickness ratio of each layer (inner layer:). Intermediate layer: outer layer) = 1: 1: 1) was obtained. Next, the printed layer surface of the antistatic biaxially stretched polyethylene terephthalate film and the inner layer surface of the laminated polyethylene film derived from the biomass are bonded to a two-component curable adhesive (manufactured by Mitsui Chemicals, Inc., A-969V / A-5). ) Was used to obtain a laminate 1 in which a base material layer, a printing layer, an adhesive layer, and a sealant layer (inner layer, intermediate layer, outer layer) were laminated in this order.

[Comparative Example 1]
<Manufacturing of laminated body 2>
The laminate 2 was obtained in the same manner as in Example 1 except that the antistatic biaxially stretched polyethylene terephthalate film of the base material layer was changed to a biaxially stretched polyethylene terephthalate film (thickness 12 μm) containing no antistatic agent. rice field.

<Manufacturing of pouch>
The laminate obtained in Example 1 was used as a wall surface film and a bottom film, the sealant layers were heat-sealed, and a linear low-density polyethylene chuck tape (manufactured by Idemitsu Unitech Co., Ltd., trade name) was further applied to the upper part. : LL-217) was attached to prepare a standing pouch with a chuck tape shown in FIG. Similarly, the standing pouch shown in FIG. 3 was prepared using the laminate obtained in Comparative Example 1.

<Antistatic performance test>
Each pouch obtained above was filled with flour, heat-sealed and sealed. Next, after opening the upper part of these pouches and removing the fitting of the chuck tape, it was confirmed how much the flour adhered to the inner surface near the opening of the pouch when the flour was taken out by tilting the opening at an angle. .. As a result, in Example 1, the amount of flour adhering to the inner surface of the pouch could be reduced as compared with Comparative Example 1.

10, 20 Laminated body 11, 21 Base material layer 12, 22 Sealant layer 13, 23 Inner layer 14, 24 Intermediate layer 15, 25 Outer layer 26 Printing layer 27 Adhesive layer 30 Packaging bag 31, 31'Wall film 32 Bottom film 32a, 32b Bottom film notch 33 Bottom film folded part 34 Bottom seal part 35a, 35b Side seal part 36 Top seal part 37 Chuck tape 38 Cut line 39a, 39b Notch

Claims (9)

A laminate including at least a base material layer and a sealant layer in this order.
The laminate has antistatic performance and
The sealant layer has a three-layer structure of an inner layer, an intermediate layer, and an outer layer in order from the base material layer side.
The intermediate layer of the sealant layer contains a linear low density polyethylene derived from biomass and contains.
A laminated body in which the thickness of the entire sealant layer is 40 μm or more and 70 μm or less. The laminate according to claim 1, wherein the intermediate layer of the sealant layer further contains linear low-density polyethylene derived from fossil fuel. The laminate according to claim 1 or 2, wherein the inner and outer layers of the sealant layer contain linear low-density polyethylene derived from fossil fuel. The laminate according to any one of claims 1 to 3, wherein the intermediate layer of the sealant layer has a biomass degree of 50% or more and 95% or less. The laminate according to any one of claims 1 to 4, wherein the biomass degree of the entire sealant layer is 10% or more and 35% or less. The laminate according to any one of claims 1 to 5, wherein the base material layer contains an antistatic agent. The laminate according to any one of claims 1 to 6, wherein the laminate further includes a printing layer between the base material layer and the sealant layer. The laminate according to claim 7, wherein the laminate further includes an adhesive layer between the print layer and the sealant layer. A packaging bag comprising the laminate according to any one of claims 1 to 8.

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