JP2018171781A - Laminate and packaging bag having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate with an improved biomass degree, capable of producing a packaging bag excellent in hand tearability.SOLUTION: A laminate 10 includes at least a first substrate layer 11, a vapor-deposited layer 12, a second substrate layer 15, and a sealant layer 17 in this order. The laminate 10 includes a printed layer 14 between the first substrate layer 11 and the second substrate layer 15, and an adhesive layer 13 between the printed layer 14 and the vapor-deposited layer 12. In the laminate 10, the sealant layer 17 includes a linear low-density polyethylene derived from a biomass and a low-density polyethylene. The laminate 10 is capable of producing a packaging bag excellent in hand tearability.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate including at least a first base material layer, a vapor deposition layer, a second base material layer, and a sealant layer in this order. Furthermore, it is related with a packaging bag provided with this laminated body.

  In recent years, with the growing demand for the establishment of a recycling-oriented society, the use of biomass has been attracting attention in the materials field, as it is desired to move away from fossil fuels as well as energy. Biomass is an organic compound photo-synthesized from carbon dioxide and water, and by using it, it is so-called carbon neutral renewable energy that becomes carbon dioxide and water again. In recent years, biomass plastics using these biomasses as raw materials have been rapidly put into practical use, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA) produced via lactic acid fermentation has begun, but it is biodegradable, and its performance as a plastic is now a general-purpose plastic. Therefore, it has not been widely used due to its limitations in product applications and product manufacturing methods. Moreover, life cycle assessment (LCA) evaluation is performed for PLA, and discussion is made on energy consumption at the time of PLA production, equivalence at the time of replacement of general-purpose plastics, and the like.

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

JP 2012-251006 A

  The present inventors, together with polyolefins produced using ethylene obtained from conventional fossil fuels (hereinafter sometimes simply referred to as “polyolefins derived from fossil fuels”), biomass polyolefins using biomass-derived ethylene as a raw material By using (hereinafter, sometimes simply referred to as “biomass polyolefin”), a packaging bag having an increased biomass degree was developed while suppressing costs. In the process, the present inventors mixed a linear low density polyethylene derived from biomass and a linear low density polyethylene derived from fossil fuel to form a sealant layer, or printed on the vapor deposition layer. I faced a technical problem that I couldn't get enough hand cutting performance when I applied it directly. Therefore, the present inventors have found the layer structure of a laminate capable of producing a packaging bag having excellent hand cutting properties as a result of further studies, and have completed the present invention.

  Therefore, the objective of this invention is providing the laminated body which can manufacture the packaging bag excellent in hand cutting property, raising the degree of biomass.

According to a first aspect of the invention,
A laminate comprising at least a first base material layer, a vapor deposition layer, a second base material layer, and a sealant layer in this order;
The laminate includes a printing layer between the first base material layer and the second base material layer, and an adhesive layer between the printing layer and the vapor deposition layer,
There is provided a laminate in which the sealant layer includes biomass-derived linear low density polyethylene and low density polyethylene.

  In the first aspect of the present invention, at least the first base material layer, the vapor deposition layer, the adhesive layer, the printing layer, the second base material layer, and the sealant layer are combined. In order, it is preferable that the vapor deposition layer is a transparent vapor deposition film.

  In the 1st aspect of this invention, it is preferable that content of the low density polyethylene in the said sealant layer is 5 to 25 mass%.

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

  In the 1st aspect of this invention, it is preferable that the said sealant layer contains 75 to 95 mass% in total of the linear low density polyethylene derived from the said biomass and / or a fossil fuel.

  In the 1st aspect of this invention, it is preferable that the biomass degree of the said sealant layer is 5% or more and 30% or less.

  In the first aspect of the present invention, the first base material layer preferably contains polyethylene terephthalate.

  In the first aspect of the present invention, the second base material layer preferably contains polyamide.

  In the 1st aspect of this invention, it is preferable to provide a gas-barrier coating film on the surface of the said vapor deposition layer.

  In the 2nd aspect of this invention, a packaging bag provided with the said laminated body is provided.

  The laminate according to the present invention includes at least a first substrate layer, a vapor deposition layer, a second substrate layer, and a sealant layer in this order, and the laminate includes the first substrate layer and the second substrate layer. A printing layer is provided between the base material layers, and an adhesive layer is provided between the printing layer and the vapor deposition layer, and the sealant layer includes biomass-derived linear low-density polyethylene and low-density polyethylene. Thus, it is possible to produce a packaging bag with excellent hand cutting properties while increasing the degree of biomass.

It is a schematic cross section which shows an example of the laminated body by this invention. It is a schematic cross section which shows an example of the laminated body by this invention. It is a model front view which shows an example of the four-sided bag by this invention.

<Laminate>
The laminate according to the present invention includes at least a first base material layer, a vapor deposition layer, a second base material layer, and a sealant layer in this order, and the first base material layer and the second base material. A printing layer is provided between the layers, and an adhesive layer is provided between the printing layer and the vapor deposition layer. The laminate may further include an adhesive layer, a gas barrier coating film, other layers, and the like. When the laminate includes two or more other layers, each may have the same composition or a different composition.

The laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of the laminate according to the present invention are shown in FIGS.
The laminated body 10 shown in FIG. 1 includes a first base material layer 11, a vapor deposition layer 12, an adhesive layer 13, a printing layer 14, a second base material layer 15, an adhesive layer 16, and a sealant layer 17. Are provided in this order. As for the packaging bag provided with the laminated body 10, the sealant layer 17 is located in the inner surface side. The vapor deposition layer 12 can be a transparent vapor deposition film.
The laminate 20 shown in FIG. 2 includes a first base layer 21, a printed layer 24, an adhesive layer 23, a vapor deposition layer 22, a second base layer 25, an adhesive layer 26, and a sealant layer 27. Are provided in this order. As for the packaging bag provided with the laminated body 10, the sealant layer 27 is located in the inner surface side. The vapor deposition layer 22 may be a transparent vapor deposition film or a metal vapor deposition film.
Hereinafter, each layer which comprises a laminated body is demonstrated.

[Base material layer]
The laminated body by this invention is equipped with a 1st base material layer and the 2nd base material layer located inside a laminated body at least. By providing at least two base material layers, hand cutting properties and strength can be improved when a packaging bag is manufactured.

  The first base layer can be a resin layer containing polyester, and is preferably a resin layer containing polyethylene terephthalate. The first base material layer is preferably stretched, and more preferably biaxially stretched. Since water resistance improves by providing a polyethylene terephthalate resin layer as a 1st base material layer, the boil sterilization tolerance of the packaging bag for boil sterilization can be improved. Moreover, hand tearability can be improved by providing a polyethylene terephthalate resin layer as a 1st base material layer.

  The polyethylene terephthalate used for the first substrate layer may be derived from biomass or derived from fossil fuel. The first base layer may include both biomass-derived polyethylene terephthalate and fossil fuel-derived polyethylene terephthalate. The biomass degree of the whole laminated body can be improved by using biomass-derived polyethylene terephthalate as at least a part of the first base material layer. Biomass-derived polyethylene terephthalate is polyethylene terephthalate having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit.

  The second base material layer can be a resin layer containing polyamide such as nylon and polyester such as polyethylene terephthalate, and is preferably a resin layer containing polyamide. The second base material layer is preferably stretched, and more preferably biaxially stretched. Examples of the polyamide include nylon 6, nylon 6,6, nylon 9, nylon 11, nylon 12, nylon 6/66, nylon 66/610, nylon MXD6, and the like. By providing a polyamide resin layer inferior in water resistance as the second layer inside the laminated body instead of outside, the strength required of the packaging bag can be improved without impairing the water resistance.

When the first substrate layer is a stretched polyethylene terephthalate film, the stretched polyethylene terephthalate film used for the first substrate layer has a tensile strength in the MD direction of preferably 150 MPa or more and 300 MPa or less, more preferably 200 MPa or more and 300 MPa or less, In the TD direction, 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. In the TD direction, it is preferably 50% or more and 250% or less, more preferably 60% or more and 200% or less.
When the second base material layer is a stretched nylon film, the stretched nylon film used for the second base material layer has a tensile strength in the MD direction, preferably 150 MPa to 350 MPa, more preferably 200 MPa to 300 MPa, TD direction. Preferably, 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, more preferably 70% or more and 150% or less in the MD direction. In the TD direction, it is preferably 30% to 200%, more preferably 50% to 150%. Moreover, when a 2nd base material layer is an extending | stretching polyethylene terephthalate film, tensile strength and tensile elongation can be made the same as a 1st base material layer.
The tensile strength and tensile elongation can be measured in accordance with JIS K 7127.

  Each of the first and second base material layers preferably has a thickness of 5 μm or more and 40 μm or less, more preferably 8 μm or more and 25 μm or less. The thicknesses of the first and second base material layers may be different or the same. If the thicknesses of the first and second base material layers are in the above range, the molding process is easy, and it can be suitably used as a packaging material.

[Sealant layer]
The laminate according to the present invention includes a sealant layer that is an innermost layer when a packaging bag is manufactured. The sealant layer includes biomass-derived linear low density polyethylene (LLDPE) and low density polyethylene (LDPE), and may further include a linear low density polyethylene derived from fossil fuel. Further, the low density polyethylene may be derived from biomass or derived from fossil fuel.

  The content of low-density polyethylene in the sealant layer (when two types derived from biomass and fossil fuel are included, the total content) is preferably 5% by mass to 25% by mass, more preferably 10% by mass to 20%. It is below mass%. In addition, the content of the linear low density polyethylene derived from biomass and / or fossil fuel in the sealant layer (when two types are included, the total content) is preferably 75% by mass to 95% by mass, and more Preferably they are 80 mass% or more and 90 mass% or less. By mixing the low density polyethylene and the linear low density polyethylene in the above ratio in the sealant layer, it is possible to achieve both excellent boil resistance and excellent hand cutting properties when the packaging bag is manufactured.

  The sealant layer preferably has a biomass degree of 5% to 30%, more preferably 10% to 25%, and still more preferably 15% to 20%. In addition, in this invention, "biomass degree" shows the weight ratio of a biomass origin component. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced while reducing costs, and the environmental load can be reduced.

The “biomass degree” (carbon concentration derived from biomass) is a value of C14 content obtained by a radioactive carbon (C14) measurement method based on ASTM-D6866. Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, corn, is also about 105.5 pMC. It is known. It is also known that fossil fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all carbon atoms in the sealant layer. In the present invention, the biomass-derived carbon content Pbio when the content of C14 in the sealant layer is PC14 can be obtained as follows.
Pbio (%) = PC14 / 105.5 × 100
Note that PMC is an abbreviation for Percent Modern Carbon.

  Biomass polyethylene is a monomer polymer containing biomass-derived ethylene. Since ethylene derived from biomass is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass. The content of ethylene derived from biomass in the raw material monomer is not necessarily 100% by mass, and is preferably 50% or more, more preferably 80% or more, for example. The raw material monomer may contain fossil fuel-derived ethylene, and may contain α-olefin monomers such as butylene, hexene, and octene. Even in such a case, the obtained polymer is called biomass polyethylene. By including an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be 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 biomass-derived fermented ethanol obtained from plant raw materials. A plant raw material is not specifically limited, A conventionally well-known plant can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

  In the present invention, biomass-derived fermented ethanol refers to ethanol that has been purified after contacting a microorganism-producing product or a crushed product thereof with a culture solution containing a carbon source obtained from plant raw materials. For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and azeotropically 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 low pressure polymerization (gas phase polymerization using Ziegler-Natta catalyst or liquid phase polymerization using metallocene catalyst). . The low density polyethylene is obtained by polymerizing ethylene by a high pressure polymerization method. Linear low density polyethylene has many short molecular chains in the molecular chain and is excellent in sealing performance.

Linear low density polyethylene and low density polyethylene is less than 0.93 g / cm ^3, preferably 0.91 g / cm ³ or more 0.93 g / cm less than ^3, more preferably 0.912 g / cm ³ or more 0.928g / Cm ³ or less, more preferably 0.915 g / cm ³ or more and 0.925 g / cm ³ or less. The MFR of linear low density polyethylene may be lower than the MFR of low density polyethylene. The density of the linear low density polyethylene and the low density polyethylene is a value measured according to the method defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. If the density of the linear low density polyethylene and the low density polyethylene is 0.91 g / cm ³ or more, the rigidity of the sealant layer containing the linear low density polyethylene and the low density polyethylene can be increased, and the inner layer of the packaging bag It can be used suitably. Moreover, if the density of linear low density polyethylene and low density polyethylene is less than 0.93 g / cm < ³ >, the mechanical strength of a sealant layer can be raised and it can use suitably as an inner layer of a packaging bag.

  The linear low density polyethylene and the low density polyethylene are 0.1 g / 10 min or more and 10 g / 10 min or less, preferably 0.2 g / 10 min or more and 9 g / 10 min or less, more preferably 1 g / 10 min or more and 8. It has a melt flow rate (MFR) of 5 g / 10 min or less. The MFR of linear low density polyethylene may be lower than the MFR of low density polyethylene. 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 defined in JIS K7210-1995. If the MFR of the linear low density polyethylene and the low density polyethylene is 0.1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if the MFR of the linear low density polyethylene and the low density polyethylene is 10 g / 10 min or less, the mechanical strength of the sealant layer can be increased.

In the present invention, biomass polyethylene suitably used is a biomass-derived linear low-density polyethylene (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 minutes) manufactured by Braschem. , Biomass degree 87%), biomass-derived linear low density polyethylene (trade name: SLL318, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min, biomass degree 87%), A linear low-density polyethylene derived from biomass manufactured by Braschem (trade name: SLH218, density: 0.916 g / cm ³ , MFR: 2.3 g / 10 min, biomass degree 87%), derived from biomass manufactured by Braschem low-density polyethylene (trade name: SBC818, ^{density: 0.918g / cm 3, MFR:} 8.1g / 10 minutes, Biomass of 95%), Braskem manufactured by low-density polyethylene (trade name derived biomass: SPB681, ^{Density: 0.922g / cm 3, MFR:} 3.8g / 10 min, the biomass of 95%), manufactured by Braskem Inc. Biomass-derived low density polyethylene (trade name: STN7006, density: 0.923 g / cm ³ , MFR: 0.6 g / 10 min, biomass degree 95%), and the like.

  Biomass-derived linear low-density polyethylene is produced, for example, using sugarcane as a raw material. The degree of dispersion of such a low-density polyethylene derived from sugarcane can be 4 or more and 7 or less. On the other hand, the degree of dispersion of the fossil-derived linear low-density polyethylene is usually from 1.5 to 3.5.

  The sealant layer preferably has a thickness of 20 μm to 80 μm, more preferably 30 μm to 70 μm, and still more preferably 40 μm to 60 μm. When the thickness of the sealant layer is within the above range, excellent hand cutting properties can be obtained when the packaging bag is manufactured.

[Deposition layer]
A vapor deposition layer can be made into the layer which consists of a transparent vapor deposition film or a metal vapor deposition film, and it is preferable that it is a layer which consists of a transparent vapor deposition film. A vapor deposition film can be formed by a conventionally well-known method, The composition and formation method are not specifically limited. When the laminate includes the vapor deposition layer, gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like can be imparted or improved. Note that the laminate may include two or more vapor deposition layers. When two or more vapor deposition layers are provided, each may have the same composition or a different composition.

  The transparent vapor deposition film is an inorganic oxide vapor deposition film. When the laminate includes a vapor deposition layer made of a transparent vapor deposition film, the gas barrier property can be imparted or improved while maintaining the permeability of the contents because it is transparent. As a transparent vapor deposition film, for example, silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium ( An evaporated film of an oxide such as Ti), lead (Pb), zirconium (Zr), or yttrium (Y) can be used. In particular, it is preferable to provide a vapor deposition film of aluminum oxide or silicon oxide for packaging bags.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1.5 for boron (B), titanium (Ti) Can take values ranging from 0 to 2, lead (Pb) from 0 to 2, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

  The thickness of the transparent vapor-deposited film of the inorganic oxide varies depending on the kind of the inorganic oxide to be used, but is, for example, arbitrarily selected and formed within a range of 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable. For example, in the case of a vapor-deposited film of aluminum oxide or silicon oxide, the film thickness is preferably 50 to 500 mm, more preferably 100 to 300 mm.

  When a laminated body is provided with the vapor deposition layer which consists of a metal vapor deposition film, gas barrier property can be provided or improved, providing or improving the light-shielding property which blocks permeation | transmission of visible light, an ultraviolet-ray, etc. As a metal vapor deposition film, for example, aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), gold ( A vapor-deposited film of a metal such as Au) or chromium (Cr) can be used. In particular, for packaging bags, it is preferable to provide an aluminum vapor deposition film.

  The film thickness of the metal vapor deposition film varies depending on the type of metal used and the like, but for example, it is desirably selected and formed within a range of 50 to 2000 mm, preferably 100 to 1000 mm. More specifically, in the case of an aluminum vapor deposition film, the film thickness is 50 to 600 mm, more preferably 100 to 450 mm.

  The said transparent vapor deposition film or metal vapor deposition film can be formed in the base material layer etc. using the following formation methods. As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

(Gas barrier coating film)
If necessary, a gas barrier coating film may be provided on the deposited film. The gas barrier coating film is a layer that functions as a layer that suppresses permeation of oxygen gas, water vapor, and the like. The gas barrier coating film has a general formula R ¹ _n M (OR ² ) _m (wherein R ¹ and R ² represent an organic group having 1 to 8 carbon atoms, M represents a metal atom, and n Represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents a valence of M.), at least one alkoxide represented by: It is obtained by a gas barrier composition containing an ethylene-vinyl alcohol copolymer and polycondensed by a sol-gel method in the presence of a sol-gel method catalyst, an acid, water, and an organic solvent.

As the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , at least one kind of a partial hydrolyzate of alkoxide and a condensate of hydrolysis of alkoxide can be used. Moreover, as a partial hydrolyzate of said alkoxide, all the alkoxy groups do not need to be hydrolyzed, The thing by which 1 or more was hydrolyzed, and its mixture may be sufficient. As a condensate of hydrolysis of alkoxide, a dimer or more of partially hydrolyzed alkoxide, specifically, a 2 to 6 mer is used.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , as the metal atom represented by M, silicon, zirconium, titanium, aluminum, and the like can be used. In the present embodiment, examples of preferable metals include silicon and titanium. In the present invention, alkoxides may be used alone or in combination of two or more different metal atom alkoxides in the same solution.

In the alkoxide represented by the above general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ¹ include, for example, a methyl group, an ethyl group, an n-propyl group, i Examples thereof include alkyl groups such as -propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n-octyl group and others. In the alkoxide represented by the general formula R ¹ _n M (OR ² ) _m , specific examples of the organic group represented by R ² include, for example, a methyl group, an ethyl group, an n-propyl group, i -Propyl group, n-butyl group, sec-butyl group, and the like. These alkyl groups in the same molecule may be the same or different.

  When preparing the gas barrier composition, for example, a silane coupling agent may be added. As said silane coupling agent, known organic reactive group containing organoalkoxysilane can be used. In this embodiment, an organoalkoxysilane having an epoxy group is particularly preferably used. Specifically, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane or the like can be used. The above silane coupling agents may be used alone or in combination of two or more.

[Print layer]
The printed layer can be used to display decorations, contents, display of the best-before period, display of manufacturers, sellers, etc., and display of other characters and letters, numbers, pictures, figures, symbols, patterns, etc. It is a layer for forming a desired arbitrary printed pattern. The print layer may be provided on the entire surface of the first base material layer or the second base material layer, or may be provided on a part thereof. A printing layer can improve hand cutting property and barrier property by not providing directly on a vapor deposition layer. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited.

  The printed layer preferably has a thickness of 0.1 μm to 10 μm, more preferably 1 μm to 5 μm, and still more preferably 1 μm to 3 μm.

[Adhesive layer]
An adhesive layer is provided between the first base material layer and the second base material layer. The adhesive layer can be formed by applying and drying an adhesive on the surface of the layer to be laminated when two layers are bonded by the dry laminating method. Examples of the adhesive include one-part or two-part cured or non-cured vinyl, (meth) acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, etc. An adhesive such as a solvent type, an aqueous type, or an emulsion type can be used. As a two-component curable adhesive, a cured product of a polyol and an isocyanate compound can be used. As a coating method of the adhesive for laminating, for example, direct gravure roll coating method, gravure roll coating method, kiss coating method, reverse roll coating method, fountain method, transfer roll coating method, and other methods can be used. .

[Adhesive layer]
The adhesive layer is a layer provided when two arbitrary layers are bonded, and can be provided between the second base material layer and the sealant layer.

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

  The adhesive layer may be an adhesive resin layer used when two layers are bonded by a sand lamination method. Examples of the thermoplastic resin that can be used for the adhesive resin layer include a polyethylene resin, a polypropylene resin, or a cyclic polyolefin resin, or a copolymer resin, a modified resin, or a mixture (including alloy) containing these resins as a main component. ) Can be used. Examples of polyolefin resins 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, ethylene / polypropylene random or block copolymer, 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 interlayer adhesion In order to improve the , It can be used acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and an acid-modified polyolefin resin modified with an unsaturated carboxylic acid such as itaconic acid. Further, a resin obtained by graft polymerization or copolymerization of an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, or an ester monomer can be used as the polyolefin resin. These materials can be used alone or in combination of two or more. As the cyclic polyolefin-based resin, for example, cyclic polyolefins such as ethylene-propylene copolymer, polymethylpentene, polybutene, and polynorbornene can be used. These resins can be used alone or in combination. In addition, as said polyethylene-type resin, what used the above ethylene derived from biomass as a monomer unit can be used, and a biomass degree can further be improved.

  When the adhesive resin layer is laminated by the melt extrusion laminating method, an anchor coat layer formed by applying an anchor coat agent and drying it may be provided on the surface of the layer to be laminated. Examples of the anchor coating agent include an anchor coating agent made of any resin having a heat resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or a polyethyleneimine. An anchor coating agent that is a cured product of a polyacrylic or polymethacrylic resin (polyol) having two or more hydroxyl groups and an isocyanate compound as a curing agent can be preferably used. Moreover, a silane coupling agent may be used in combination as an additive, and nitrified cotton may be used in combination in order to improve heat resistance.

  There may be one adhesive layer in the laminate, or two or more may be included. 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 adhesive layer after drying has a thickness of 1 μm to 10 μm, preferably 2 μm to 5 μm. The adhesive resin layer has a thickness of 5 μm to 50 μm, preferably 10 μm to 30 μm. The anchor coat layer after drying 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.

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

<Method for producing laminate>
The manufacturing method of the laminated body by this invention is not specifically limited, It can manufacture using conventionally well-known methods, such as a dry lamination method and a sand lamination method.

  The laminate according to the present invention is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). Further, the laminate according to the present invention can be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-processing processing to produce a molded product.

<Packaging bag>
The packaging bag by this invention is equipped with the said laminated body, and can be used conveniently for boil sterilization. For example, the above laminate is used and is folded in two, or two laminates are prepared, the sealant layers face each other and overlap each other, and the peripheral edge thereof is, for example, a side seal. Type, two-side seal type, three-side seal type, four-side seal type, envelope-attached seal type, joint-attached seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. Various forms of packaging bags can be manufactured by heat sealing according to the form.

  In the above, as a 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.

  The packaging bag has excellent hand cutting properties while exhibiting a high degree of biomass, and can further impart boil sterilization resistance. For example, food and drink, fruit juice, juice, drinking water, liquor, It can be suitably used as a package for various foods and beverages such as cooked foods, marine products, frozen foods, meat products, boiled foods, rice cakes, liquid soups and seasonings, liquid detergents, cosmetics, and chemical products. .

The packaging bag by this invention is demonstrated referring drawings. An example of a schematic front view of a four-sided bag according to the present invention is shown in FIG.
The four-sided bag 30 shown in FIG. 3 is arranged with the sealant layers of the wall surface films (using the above laminated body) 31 and 31 ′ facing each other, and heat-sealing the three end portions other than the upper part around the outer periphery. A peripheral seal portion 32 is formed. After filling the contents 33 from the upper opening, for example, after deaeration, the upper end part is heat sealed to form the upper end seal part 34, whereby the four-sided bag 30 sealing the contents 33 is obtained. can get. In the above-described example, the example in which the four-sided bag 30 is configured using two wall surface films has been described, but the packaging bag may be configured using one film.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.

[Example 1]
<Preparation of laminated body 1>
A biaxially stretched nylon film (thickness 15 μm, manufactured by Unitika Ltd., trade name: Emblem ONBC) was prepared as a second base material layer, and a printing layer was formed on one surface of the nylon film by gravure printing. Subsequently, a biaxially stretched polyethylene terephthalate film derived from fossil fuel (thickness 12 μm, Mitsubishi resin (1 μm), which is the first base material layer on which the printed surface of the nylon film and a vapor-deposited film of silicon oxide were formed using the PVD method. A laminated film 1 is obtained by bonding the vapor-deposited surface of a product name, Tech Barrier VX) using a two-component curable adhesive (Rock Paint Co., Ltd., RU-40 / H-5). It was. In addition, 60 parts by mass of fossil fuel-derived linear low density polyethylene (softening point: 108 ° C., density: 0.918 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree: 0%), fossil fuel Low-density polyethylene (softening point: 93 ° C., density: 0.924 g / cm ³ , MFR: 2.0 g / 10 min, biomass degree: 0%) 20 parts by mass, and linear low-density polyethylene derived from biomass (Softening point: 112 ° C., manufactured by Brasschem, trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 min, biomass degree 87%) A composition was obtained. Subsequently, the obtained resin composition was formed into a film by a top-blown air-cooled inflation co-extrusion film forming machine to obtain a polyethylene film 1 for a sealant layer (thickness 60 μm, biomass degree: 17.4%). Next, the nylon film surface of the laminated film 1 and the polyethylene film 1 are bonded together using a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5). A laminate 1 was obtained in which a material layer, a vapor deposition layer, an adhesive layer, a printing layer, a second base material layer, an adhesive layer, and a sealant layer were sequentially laminated.

[Example 2]
<Preparation of laminated body 2>
The blend of the polyethylene film 1 for the sealant layer is added to 70 parts by mass of linear low density polyethylene derived from fossil fuel, 10 parts by mass of low density polyethylene derived from fossil fuel, and 20 parts by mass of linear low density polyethylene derived from biomass. Except having changed, it carried out similarly to Example 1, and obtained the laminated body 2. FIG.

[Example 3]
<Preparation of laminate 3>
The blend of the polyethylene film 1 for the sealant layer is added to 55 parts by mass of linear low density polyethylene derived from fossil fuel, 25 parts by mass of low density polyethylene derived from fossil fuel, and 20 parts by mass of linear low density polyethylene derived from biomass. Except having changed, it carried out similarly to Example 1, and obtained the laminated body 3. FIG.

[Example 4]
<Preparation of laminate 4>
A biaxially stretched nylon film (thickness 15 μm, manufactured by Unitika Ltd., trade name: Emblem ONBC) was prepared as a second base material layer, and silicon oxide was deposited on one surface of the nylon film by a CVD method. Moreover, the printing layer was formed by gravure printing on one surface of the biaxially-stretched polyethylene terephthalate film (thickness 12 micrometers) derived from the fossil fuel which is a 1st base material layer. Subsequently, the vapor deposition surface of the nylon film and the printing surface of the polyethylene terephthalate film are bonded together using a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5), and laminated. Film 2 was obtained. Next, the nylon film surface of the laminated film 2 and the polyethylene film 1 are bonded together using a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5). A laminate 4 was obtained in which a base material layer, a printing layer, an adhesive layer, a vapor deposition layer, a second base material layer, an adhesive layer, and a sealant layer were sequentially laminated.

[Comparative Example 1]
<Preparation of laminated body 5>
Gravure on the vapor-deposited surface of a biaxially stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Mitsubishi Plastics Co., Ltd., trade name: Techbarrier VX) derived from fossil fuel, which is the first base material layer on which a silicon oxide vapor deposition film is formed. A printing layer was formed by printing. Subsequently, the printing surface of the polyethylene terephthalate film and the biaxially stretched nylon film (thickness 15 μm, manufactured by Unitika Ltd., trade name: Emblem ONBC) as the second base material layer are two-component curable adhesive (lock paint). The laminated film 3 was obtained by pasting together using RU-40 / H-5). Next, the nylon film surface of the laminated film 3 and the polyethylene film 1 are bonded together using a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5). A laminate 5 was obtained in which a base material layer, a vapor deposition layer, a printing layer, an adhesive layer, a second base material layer, an adhesive layer, and a sealant layer were sequentially laminated.

[Comparative Example 2]
<Preparation of laminate 6>
The first base material layer on which the silicon oxide vapor deposition film is formed is a biaxially stretched polyethylene terephthalate film (thickness 12 μm, manufactured by Mitsubishi Plastics Co., Ltd., trade name: Techbarrier VX) derived from fossil fuel and A biaxially stretched nylon film (thickness 15 μm, manufactured by Unitika Co., Ltd., trade name: Emblem ONBC), which is a two-substrate layer, is a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5). ) To obtain a laminated film 4. Next, a printed layer was formed on the nylon film surface of the laminated film 4 by gravure printing to obtain a laminated film 5. Next, the printed surface of the laminated film 5 and the polyethylene film 1 are bonded together using a two-component curable adhesive (Rock Paint Co., Ltd., RU-40 / H-5), and the first substrate layer Thus, a laminate 6 was obtained in which a vapor deposition layer, an adhesive layer, a second base material layer, a printing layer, an adhesive layer, and a sealant layer were sequentially laminated.

<Manufacture of packaging bags>
The laminate obtained in Example 1 was used as a wall film, the sealant layers were arranged to face each other, and the peripheral edge and the upper end were heat sealed to produce a four-sided bag shown in FIG. Similarly, the four-sided bag shown in FIG. 3 was produced using the laminated body obtained in Examples 2-4 and Comparative Examples 1-2.

<Hand cutting test>
The hand cutting property when the four-sided bag obtained above was cut was confirmed.
(Evaluation criteria)
○: It was possible to cut without applying excessive force.
X: It was not possible to cut unless excessive force was applied.

The results of the performance evaluation test are shown in Table 1.

10, 20 Laminate 11, 21 First substrate layer 12, 22 Vapor deposition layer 13, 23 Adhesive layer 14, 24 Print layer 15, 25 Second substrate layer 16, 26 Adhesive layer 17, 27 Sealant layer 30 Four-sided bag 31, 31 'wall film (laminate)
32 peripheral seal portion 33 contents 34 upper end seal portion

Claims (10)

A laminate comprising at least a first base material layer, a vapor deposition layer, a second base material layer, and a sealant layer in this order;
The laminate includes a printing layer between the first base material layer and the second base material layer, and an adhesive layer between the printing layer and the vapor deposition layer,
A laminate in which the sealant layer includes biomass-derived linear low-density polyethylene and low-density polyethylene. At least the first base layer, the vapor deposition layer, the adhesive layer, the printing layer, the second base layer, and the sealant layer in this order,
The laminated body of Claim 1 whose said vapor deposition layer is a transparent vapor deposition film.   The laminate according to claim 1 or 2, wherein the content of the low density polyethylene in the sealant layer is 5% by mass or more and 25% by mass or less.   The laminated body as described in any one of Claims 1-3 in which the said sealant layer further contains the linear low density polyethylene derived from a fossil fuel.   The laminate according to claim 4, wherein the sealant layer contains a total of 75% by mass or more and 95% by mass or less of linear low density polyethylene derived from the biomass and / or fossil fuel.   The laminated body as described in any one of Claims 1-5 whose biomass degree of the said sealant layer is 5% or more and 30% or less.   The laminate according to any one of claims 1 to 6, wherein the first base material layer includes polyethylene terephthalate.   The laminate according to any one of claims 1 to 7, wherein the second base material layer contains polyamide.   The laminated body as described in any one of Claims 1-8 provided with a gas-barrier coating film on the surface of the said vapor deposition layer.   A packaging bag provided with the laminated body as described in any one of Claims 1-9.

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