JP2018171895A - Laminate and packaging bag having the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body capable of producing a packaging bag having excellent impact resistance and hand-cutting property while improving the degree of biomass. A laminate 10 according to the present invention includes at least a first base material layer 11, a metal vapor deposition layer 12, a second base material layer 13, and a sealant layer 14, and the first base material layer is a polyamide. The second base material layer contains polyethylene terephthalate, the sealant layer contains linear low-density polyethylene derived from biomass and low-density polyethylene, and the thickness of the sealant layer is 30 μm or more and 150 μm or less. Such a laminate can produce a packaging bag having excellent impact resistance and hand-cutting property. [Selection diagram] Fig. 1

Description

  The present invention relates to a laminate including at least a first base material layer, a metal 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, when the present inventors mixed two kinds of linear low density polyethylene derived from biomass and linear low density polyethylene derived from fossil fuel to form a sealant layer of a packaging bag, I faced the technical challenge of not being able to achieve a balance between sexuality and hand cutting. Thus, as a result of further studies, the present inventors have found a layer structure of a laminate capable of producing a packaging bag excellent in impact resistance and hand cutting properties, 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 impact resistance and 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 metal vapor deposition layer, a second base material layer, and a sealant layer in this order;
The first base layer includes polyamide;
The second substrate layer comprises polyethylene terephthalate;
The sealant layer includes biomass-derived linear low density polyethylene and low density polyethylene,
A laminate having a thickness of the sealant layer of 30 μm or more and 150 μm or less is provided.

  In the first aspect of the present invention, the sealant layer preferably contains 5% by mass or more and 25% by mass or less of the low density polyethylene.

  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 metal vapor deposition layer is preferably an aluminum vapor deposition layer.

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

  In the first aspect of the present invention, the laminate further includes an adhesive layer between the first base material layer and the metal vapor deposition layer and / or between the second base material layer and the sealant layer. It is preferable.

  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 base material layer containing polyamide, a metal vapor deposition layer, a second base material layer containing polyethylene terephthalate, and a sealant layer in this order, and the sealant layer is derived from biomass. A packaging bag that includes linear low-density polyethylene and low-density polyethylene, and that has a thickness of the sealant layer of 80 μm or more and 150 μm or less, and has excellent impact resistance and hand cutting properties while increasing the degree of biomass. Can be manufactured.

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 refilling pouch by this invention. It is a figure which shows the list of the layer structure of the laminated bodies 1-9 created in Examples 1-7 and Comparative Examples 1-2.

<Laminate>
The laminated body by this invention is equipped with a 1st base material layer, a metal vapor deposition layer, a 2nd base material layer, and a sealant layer in this order at least. The laminate may further include a printed layer, an adhesive layer, 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 is provided with the 1st base material layer 11, the metal vapor deposition layer 12, the 2nd base material layer 13, and the sealant layer 14 in this order. As for the packaging bag provided with the laminated body 10, the sealant layer 14 is located in the inner surface side.
The laminated body 20 shown in FIG. 2 includes a first base layer 21, a printed layer 25, an adhesive layer 26, a metal deposition layer 22, a second base layer 23, an adhesive layer 27, and a sealant layer 24. Are provided in this order. As for the packaging bag provided with the laminated body 20, the sealant layer 24 is located in the inner surface side.
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 can be improved when a packaging bag is manufactured.

  The first base material layer is a resin layer containing polyamide. The first base material layer is preferably stretched and 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 the polyamide resin layer as the first base material layer, the puncture strength and the like can be improved when the packaging bag is manufactured.

  The second base material layer is a resin layer containing polyethylene terephthalate. The second base material layer is preferably stretched and is preferably biaxially stretched. By providing the polyethylene terephthalate resin layer as the second layer located inside the laminate, it is possible to improve the hand cutting property required for the packaging bag.

  The polyethylene terephthalate used for the second base material layer may be derived from biomass or derived from fossil fuel. The second base material layer may include both biomass-derived polyethylene terephthalate and fossil fuel-derived polyethylene terephthalate. The biomass degree of the whole laminate can be improved by using biomass-derived polyethylene terephthalate as at least a part of the second 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.

When the first substrate layer is a stretched nylon film, the stretched nylon film used for the first substrate 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%.
When the second substrate layer is a stretched polyethylene terephthalate film, the stretched polyethylene terephthalate film used for the second 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.
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.

[Metal deposition layer]
A metal vapor deposition layer is a layer which consists of a metal vapor deposition film. A vapor deposition film can be formed by a conventionally well-known method, and a metal composition and a formation method are not specifically limited. When the laminate includes a metal vapor deposition layer, gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light blocking properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted or improved. Moreover, since a metallic luster can be provided to a packaging bag, designability can be improved. The laminate may include two or more metal vapor deposition layers. When two or more metal vapor deposition layers are provided, each may have the same composition or a different composition.

  Examples of the deposited film include aluminum (Al), magnesium (Mg), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), and gold (Au ), A vapor-deposited film of a metal such as chromium (Cr) can be used. In particular, for packaging bags, it is preferable to provide an aluminum vapor deposition film.

  A 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.

  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.

[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. When the sealant layer contains both the biomass-derived linear low-density polyethylene and the low-density polyethylene, it is possible to achieve both excellent impact resistance and excellent hand cutting properties when a packaging bag is manufactured.

  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 impact 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%. 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.

  In the present invention, the above-mentioned “biomass degree” (carbon concentration derived from biomass) may be indicated by the value of C14 content obtained by a radioactive carbon (C14) measurement method based on ASTM-D6866, and is derived from biomass. You may show by the weight ratio of a component.

When the value obtained by measuring the content of biomass-derived carbon by measurement of radioactive carbon (C14) is shown as “biomass degree”, “biomass degree” can be obtained as follows. That is, since carbon dioxide in the atmosphere contains C14 at a constant rate (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 that 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.

  For example, if all biomass-derived ethylene is used as a polyolefin raw material, the biomass-derived carbon content Pbio in the polyolefin is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Further, the content Pbio of the carbon derived from biomass in the polyolefin derived from fossil fuel produced only with the raw material derived from fossil fuel is 0%, and the biomass degree of the polyolefin derived from fossil fuel is 0%.

  Moreover, when the “biomass degree” is expressed by the weight ratio of the biomass-derived component, the “biomass degree” can be obtained as follows. For example, if all biomass-derived ethylene is used as a polyolefin raw material, the weight ratio of biomass-derived components in the polyolefin is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. Moreover, the weight ratio of the biomass origin component in the polyolefin derived from the fossil fuel manufactured only with the raw material derived from a fossil fuel is 0%, and the biomass degree of the polyolefin derived from a fossil fuel becomes 0%.

  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 has a thickness of 30 μm to 150 μm, preferably 80 μm to 150 μm, more preferably 90 μm to 140 μm, and still more preferably 100 μm to 130 μm. When the thickness of the sealant layer is in the above range, it is possible to achieve both excellent impact resistance and excellent hand cutting properties when a packaging bag is manufactured.

[Print layer]
The print layer is a layer formed by printing for display of decoration, display of contents, display of a best-before period, display of a manufacturer, a seller, etc., and the addition of aesthetics. The print layer includes a pattern layer that forms a desired arbitrary pattern such as a picture, a photograph, a character, a number, a figure, a symbol, or a pattern. The printed layer may further include a ground color layer formed by printing so as to make the pattern of the pattern layer stand out. The printed layer contains a colorant and a cured product of a polyol and an isocyanate compound. The printed layer may or may not contain a biomass-derived component. When forming a printing layer with the material containing a biomass-derived component, a printing layer can be formed using the hardened | cured material in which at least any one of the polyol as a main ingredient and the isocyanate compound as a hardening | curing agent contains a biomass-derived component. Moreover, when forming a printing layer with the material which does not contain a biomass origin component, a printing layer can be formed using the isocyanate compound which consists of a conventionally well-known fossil fuel origin component, and a fossil fuel origin component. As the polyol, a polyester polyol which is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, or a polyether polyol which is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate can be used.

[Polyester polyol]
When the polyester polyol contains a biomass-derived component, at least one of a polyfunctional alcohol and a polyfunctional carboxylic acid contains a biomass-derived component. The following examples can be given as polyester polyols containing biomass-derived components.
・ Reactant of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・ Reaction product of polyfunctional alcohol derived from fossil fuel and multifunctional carboxylic acid derived from biomass ・ Derived from multifunctional alcohol derived from biomass and fossil fuel Reactant with polyfunctional carboxylic acid

  As the polyfunctional alcohol derived from biomass, an aliphatic polyfunctional alcohol obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. As the aliphatic polyfunctional alcohol derived from biomass, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), butylene obtained from plant raw materials by the following method. There are glycol (BG) and hexamethylene glycol, and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant raw materials. Polypropylene glycol produced by a bio-method such as the fermentation method can produce useful by-products such as lactic acid from the viewpoint of safety compared to polypropylene glycol of the EO production method, and can also keep production costs low. It is also preferable that it is possible.
Biomass-derived butylene glycol can be produced by obtaining succinic acid obtained by producing glycol from plant raw materials and fermenting it and hydrogenating it.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

  As the polyfunctional alcohol derived from fossil fuel, a compound having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, the polyfunctional alcohol derived from fossil fuel is not particularly limited and conventionally known ones can be used. For example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG) , Diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, and the like can be used. These may be used alone or in combination of two or more.

  Biomass-derived polyfunctional carboxylic acids are recycled from recyclable soybean oil, linseed oil, tung oil, palm oil, palm oil, castor oil and other plant-derived oils, and waste edible oils mainly composed of them. Aliphatic polyfunctional carboxylic acids obtained from plant materials such as oil can be used. Examples of the biomass-derived aliphatic polyfunctional carboxylic acid include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced as a by-product of heptyl alcohol by alkaline pyrolysis of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

  As the polyfunctional carboxylic acid derived from fossil fuel, an aliphatic polyfunctional carboxylic acid or an aromatic polyfunctional carboxylic acid can be used. The aliphatic polyfunctional carboxylic acid derived from fossil fuel is not particularly limited, and conventionally known ones can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride Examples thereof include acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, and ester compounds thereof. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuel is not particularly limited and conventionally known ones can be used, for example, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, trimellitic acid, And pyromellitic acid, and ester compounds thereof can be used. These may be used alone or in combination of two or more.

[Polyether polyol]
When the polyether polyol contains a biomass-derived component, at least one of a polyfunctional alcohol and a polyfunctional isocyanate contains a biomass-derived component. The following examples can be given as polyether polyols containing biomass-derived components.
・ Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional isocyanate ・ Reaction product of polyfunctional alcohol derived from fossil fuel and polyfunctional isocyanate derived from biomass ・ Multi-functional alcohol derived from biomass and many derived from fossil fuel Reactant with functional isocyanate

  As the polyfunctional alcohol derived from biomass and the polyfunctional alcohol derived from fossil fuel, the polyfunctional alcohol derived from biomass and the polyfunctional alcohol derived from fossil fuel described in the above polyester polyol can be used.

  As a polyfunctional isocyanate derived from biomass, a plant-derived divalent carboxylic acid is acidified, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group into an isocyanate group. What was obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Examples of the diisocyanate derived from biomass include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate and the like. Moreover, plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting its amino group to an isocyanate group. For example, lysine diisocyanate (LDI) can be obtained by converting a carboxyl group of lysine into a methyl ester and then converting an amino group into an isocyanate group. 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

  Other synthesis methods of 1,5-pentamethylene diisocyanate include a phosgenation method and a carbamate method. More specifically, the phosgenation method includes a method in which 1,5-pentamethylenediamine or a salt thereof is directly reacted with phosgene, or a hydrochloride salt of pentamethylenediamine is suspended in an inert solvent and reacted with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamation method, first, 1,5-pentamethylenediamine or a salt thereof is carbamatized to form pentamethylene dicarbamate (PDC), and then thermally decomposed to obtain 1,5-pentamethylene diisocyanate. To be synthesized. In the present invention, examples of the polyisocyanate preferably used include 1,5-pentamethylene diisocyanate polyisocyanate (trade name: STAVIO (registered trademark)) manufactured by Mitsui Chemicals.

  The polyfunctional isocyanate derived from fossil fuel is not particularly limited, and conventionally known ones can be used. For example, toluene-2,4-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-isopropyl- 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanate diphenyl ether, 4,4′-methylenebis (phenylene isocyanate) (MDI), Julylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate di Aromatic diisocyanate such as Njiru the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI, and the like. These may be used alone or in combination of two or more.

[Colorant]
The colorant is not particularly limited, and conventionally known pigments and dyes can be used.

  When the printing layer contains a biomass-derived component, the printing layer preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, and further preferably 10% or more and 50% or less. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  A printing layer can be provided as needed, for example, can be provided between a 1st base material layer and a metal vapor deposition layer. The print layer may be provided on the entire surface of the first base material layer, or may be provided on a part thereof. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited.

The weight of the printed layer after drying is preferably from 0.1 g / m ^{2 to} 10 g / m ² , more preferably from 1 g / m ^{2 to} 5 g / m ² , and even more preferably from 1 g / m ^{2 to} 3 g / m ^2. It is as follows.

  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]
The adhesive layer is a layer provided when two arbitrary layers are bonded, and can be provided, for example, between the first base material layer and the metal deposition layer, or 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 the two-component curable adhesive, a cured product of a polyol and an isocyanate compound can be used, and at least one of the polyol and the isocyanate compound may contain a biomass-derived component.

  In the adhesive layer, as an isocyanate compound containing a biomass-derived component, an isocyanate compound containing a biomass-derived component similar to the above-described printed layer can be used. In the adhesive layer, as the polyol containing a biomass-derived component, the same polyol as that in the above-mentioned printing layer can be used. When both the printed layer and the adhesive layer are formed using a cured product containing a biomass-derived component, the cured product in the printed layer and the cured product in the adhesive layer may have the same composition or different compositions. good.

  The adhesive layer preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, and further preferably 30% or more and 50% or less. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  The method for forming the adhesive layer is not particularly limited. Examples of the method for coating the adhesive for laminating include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, It can be applied by the Fonten method, transfer roll coating method, or other methods.

The weight of the adhesive layer after drying is preferably from 0.1 g / m ^{2 to} 10 g / m ² , more preferably from 1 g / m ^{2 to} 6 g / m ² , and even more preferably from 2 g / m ^{2 to} 5 g / m. ² or less.

  The adhesive layer preferably has a thickness of 0.1 μm to 10 μm, more preferably 1 μm to 6 μm, and still more preferably 2 μm to 5 μm.

  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 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. The adhesive layer after drying has a thickness of 1 μm to 10 μm, preferably 2 μm to 5 μm. The adhesive resin layer preferably has a thickness of 5 μm to 50 μm, preferably 10 μm to 30 μm.

[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 provided with the said laminated body. For example, the above laminate is used, and the laminate is folded in two, or two laminates are prepared, and the surfaces of the sealant are opposed to each other, and the peripheral end portion 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. Thus, various forms of packaging bags can be manufactured.

  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.

  Since the packaging bag has excellent impact resistance and hand cutting properties while exhibiting a high degree of biomass, it can be suitably used particularly as a refill pouch for sealing and packaging shampoo, rinse, food, etc. for refill. .

The packaging bag by this invention is demonstrated referring drawings. An example of a schematic front view of a refillable pouch according to the present invention is shown in FIG.
The refill pouch 100 shown in FIG. 3 is manufactured in a standing pouch format, and the bottom portion of the pouch is placed between the lower portions of the front and rear wall films (using the above laminate) 101, 101 ′. (It may be the same as or different from the film) It is formed in a form having a gusset portion 104 formed by folding 103 inward and inserting it to the bottom film folding portion 102, and in the vicinity of the lower ends on both sides of the bottom film folded inward In this case, semi-circular bottom film cutout portions 103a and 103b are provided, and the gusset portion 104 is heat-sealed with a bottom-shaped bottom seal portion 105 that is concave in a curved line shape from both sides to the center. Form. Further, the body portion of the pouch is formed by heat-sealing the edge portions on both sides of the front and back wall films 101 and 101 ′ with the side seal portions 106 a and 106 b, and at one corner portion (see FIG. 3 on the left corner) is a tapered shape formed by heat-sealing the outer periphery with a spout portion seal portion 107 and having a narrow width and facing obliquely outwardly upward. 109b is provided in a protruding shape. In addition, a portion of the upper portion of the pouch 100 where the spout 110 is not provided is heat-sealed by the upper seal portion 108, but this portion is used as a filling port for the content. It is used as an opening of the seal, and heat sealing is performed after filling the contents. In the above-described example, the example in which the refill pouch 100 is configured using two wall films and one bottom film is described. However, the refill pouch is configured using one film or two films. You may make it do.

  Furthermore, the refilling pouch 100 includes a half-cut line 111 and a notch 112 at an upper end thereof as an easy-opening means at the opening position on the distal end side of the spout portion 110. In addition, the half-cut line 111 is shown by three parallel half-cut lines in FIG. 3, but in addition to one or two, a plurality of half-cut lines 111 such as one to three on both sides of the central half-cut line Arbitrary shape, such as a shape that converges the half-cut line in parallel or in the center half-cut line, or a combination of multiple parallel half-cut lines and diagonal half-cut lines that cross diagonally It can be provided in a shape.

  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) was prepared as a first base material layer, and a printing layer was formed on one surface of the nylon film by gravure printing. Subsequently, the printing surface of the nylon film and the vapor-deposited surface of a biaxially stretched polyethylene terephthalate film (produced by Saiichi Kogyo Co., Ltd., thickness 12 μm) derived from fossil fuel with an aluminum vapor-deposited film formed thereon are two-component curable adhesive A laminated film was obtained by pasting together using RU-40 / H-5 (manufactured by Rock Paint Co., Ltd.). In addition, 60 parts by mass of fossil fuel-derived linear low density polyethylene (density: 0.918 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree: 0%) and fossil fuel-derived low density polyethylene ( Density: 0.924 g / cm ³ , MFR: 2.0 g / 10 min, biomass degree: 0% 20 parts by mass, biomass-derived linear low density polyethylene (LLDPE, manufactured by Braschem, trade name: SLL118, 20 parts by mass of density: 0.916 g / cm ³ , MFR: 1.0 g / 10 min, biomass degree 87%) was melt-kneaded to obtain a resin composition. 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 (thickness 110 μm, biomass degree: 17.4%) for a sealant layer. Next, the biaxially stretched polyethylene terephthalate film surface of the laminated film and the polyethylene film 1 are bonded together using a two-component curable adhesive (Rock Paint Co., Ltd., RU-40 / H-5). A laminate 1 was obtained in which a first substrate layer, a printing layer, an adhesive layer, a metal vapor deposition layer, a second substrate 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 laminate 4 was obtained in the same manner as in Example 1 except that the thickness of the polyethylene film 1 for the sealant layer was changed to 80 μm.

[Example 5]
<Preparation of laminated body 5>
A laminate 5 was obtained in the same manner as in Example 1 except that the thickness of the polyethylene film 1 for the sealant layer was changed to 120 μm.

[Example 6]
<Preparation of laminate 6>
A laminate 6 was obtained in the same manner as in Example 1 except that the thickness of the polyethylene film 1 for the sealant layer was changed to 150 μm.

[Comparative Example 1]
<Preparation of laminate 7>
A laminate 7 was obtained in the same manner as in Example 1 except that the biaxially stretched nylon film of the first base material layer was changed to a biaxially stretched polyethylene terephthalate film (thickness: 12 μm).

[Comparative Example 2]
<Preparation of laminated body 8>
Except for changing the blend of the polyethylene film 1 for the sealant layer to 80 parts by mass of linear low density polyethylene derived from fossil fuel and 20 parts by mass of linear low density polyethylene derived from biomass, the same as in Example 1, A laminate 8 was obtained.

[Example 7]
<Preparation of laminated body 9>
A biaxially stretched nylon film (thickness 25 μm) was prepared as the first base material layer. Subsequently, the one surface of the nylon film and the vapor-deposited surface of a biaxially stretched polyethylene terephthalate film (produced by Saiichi Kogyo Co., Ltd., thickness 12 μm) derived from fossil fuel with an aluminum vapor-deposited film formed thereon are bonded to a two-component curable adhesive A laminated film was obtained by pasting together using an agent (Rock Paint Co., Ltd., RU-40 / H-5). In addition, the resin composition for the sealant layer obtained in Example 1 was formed into a film by a top-blown air-cooled inflation coextrusion film forming machine, and a polyethylene film for the sealant layer (thickness 40 μm, biomass degree: 17.4). %). Next, the biaxially stretched polyethylene terephthalate film surface of the laminated film and the polyethylene film for the sealant layer are bonded using a two-component curable adhesive (manufactured by Rock Paint Co., Ltd., RU-40 / H-5). In addition, a laminate 9 was obtained in which a first base material layer, an adhesive layer, a metal vapor deposition layer, a second base material layer, an adhesive layer, and a sealant layer were sequentially laminated.

  FIG. 4 shows a list of layer configurations of the laminates 1 to 9 created in Examples 1 to 7 and Comparative Examples 1 and 2. In FIG. 4, “/” represents a boundary between layers. The leftmost layer is a layer constituting the outer surface when the laminate is used as a packaging material, and the rightmost layer is a layer constituting the inner surface when the laminate is used as a packaging material. “ONy” means a nylon film. “PET” means PET film. “Mark” means a printed layer. “Contact” means an adhesive layer containing an adhesive. “Deposition layer” means a metal deposition layer. “Bio-PE” means a biomass-derived polyethylene film. “Bio-LLDPE” means biomass-derived linear low density polyethylene. “Fossil LLDPE” means linear low density polyethylene derived from fossil fuel. “Fossil LDPE” means low density polyethylene derived from fossil fuels. The numbers in the layer structure mean the layer thickness (unit: μm). The numbers in the details of bio-PE mean the blending ratio of each component.

<Manufacture of pouches>
Using the laminate obtained in Example 1 as a wall film and a bottom film, external dimensions: height 220 mm × width 130 mm, bottom folding part height 40 mm, seal width 5 mm, and the standing pouch shown in FIG. Pouch) was prepared. The bottom was heat sealed with a boat bottom type seal pattern. Similarly, the standing pouch (refillable pouch) shown in FIG. 3 was produced using the laminated body obtained in Examples 2-7 and Comparative Examples 1-2.

<Impact resistance test>
Each pouch obtained above was filled with 400 cc of water and sealed by heat sealing. Next, these pouches were repeatedly dropped 10 times from a height of 1.2 m with the bottom portion facing downward, and evaluated according to the following criteria. The evaluation results are shown in Table 1.
(Evaluation criteria)
○: The pouch did not break.
X: The pouch was broken.

<Hand cutting test>
Three standing pouches (refillable pouches) shown in FIG. 3 prepared in the same manner as described above were prepared using the laminates obtained in the examples and comparative examples. Then, the hand cutting property when cut along the half-cut line was confirmed using the notch provided in the spout part of the standing pouch as a base point.
(Evaluation criteria)
○: All three samples could be cut without applying excessive force.
X: Even one sample could not be cut unless excessive force was applied.

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

DESCRIPTION OF SYMBOLS 10, 20 Laminated body 11, 21 1st base material layer 12, 22 Metal vapor deposition layer 13, 23 2nd base material layer 14, 24 Sealant layer 25 Print layer 26, 27 Adhesive layer 100 Refillable pouch 101, 101 'Wall film 102 Bottom film folding part 103 Bottom film 103a, 103b Bottom film notch part 104 Gusset part 105 Bottom seal part 106a, 106b Side seal part 107 Outlet seal part 108 Upper seal part 109a, 109b Notch part 110 Outlet part 111 Half cut wire 112 notch

Claims (9)

A laminate comprising at least a first base material layer, a metal vapor deposition layer, a second base material layer, and a sealant layer in this order;
The first base layer includes polyamide;
The second substrate layer comprises polyethylene terephthalate;
The sealant layer includes biomass-derived linear low density polyethylene and low density polyethylene,
The laminated body whose thickness of the said sealant layer is 30 micrometers or more and 150 micrometers or less.   The laminate according to claim 1, wherein the sealant layer contains 5% by mass to 25% by mass of the low-density polyethylene.   The laminated body of Claim 1 or 2 in which the said sealant layer further contains the linear low density polyethylene derived from a fossil fuel.   The laminate according to claim 3, 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 1-4 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 5, wherein the metal deposition layer is an aluminum deposition layer.   The laminate according to any one of claims 1 to 6, wherein the laminate further comprises a printed layer between the first base material layer and the metal vapor deposition layer.   The laminated body further includes an adhesive layer between the first base material layer and the metal vapor deposition layer and / or between the second base material layer and the sealant layer. The laminate according to item.   A packaging bag provided with the laminated body as described in any one of Claims 1-8.