JP2020055567A - Packaging materia and pouch - Google Patents

Abstract

To provide a packaging material capable of reducing an environmental load and exhibiting a metal tone, and a pouch.SOLUTION: A packaging material 10-1 is formed by laminating a first polyester film 11 having a printing layer 11A, a second polyester film 13 having a metal vapor deposition layer 13A, and a sealant layer 14 in this order. This packaging material 10-1 comprises a first adhesive resin layer 12 provided between the first and second polyester films 11, 13. The first adhesive resin layer 12 includes low-density polyethylene derived from a biomass, and the sealant layer 14 includes polyethylene.SELECTED DRAWING: Figure 1

Description

  The present invention relates to packaging materials and pouches.

  In recent years, with the increasing demand for the establishment of a recycling-oriented society, in the field of packaging materials, as in the field of energy, it has been desired to break away from fossil fuels, and the use of biomass has attracted attention. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is converted into carbon dioxide and water again by using it. Recently, biomass plastics using biomass as a raw material have been rapidly commercialized, and attempts have been made to produce various resins from biomass raw materials.

  As a biomass-derived resin, commercial production of polylactic acid (PLA), which is manufactured via lactic acid fermentation, has begun, but its performance as a plastic, including its biodegradability, is the current general-purpose plastic. Therefore, there is a limit in the product use and the method of manufacturing the product, and the product has not been widely used. In addition, a life cycle assessment (LCA) evaluation is performed on the PLA, and the energy consumption at the time of manufacturing the PLA and the equivalence at the time of replacing the general-purpose plastic are discussed.

  Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyester are used. In particular, polyethylene is formed into films, sheets, bottles, and the like, and is used for various uses such as packaging materials, and is widely used worldwide. Therefore, the use of conventional fossil fuel-derived polyethylene increases the environmental burden. Therefore, it is desired to reduce the amount of fossil fuel used by using biomass-derived raw materials for producing polyethylene. For example, to date, it has been studied to produce ethylene and butylene as raw materials for polyolefin resins from renewable natural raw materials (see Patent Document 1).

JP 2011-506628 A

  At present, a first polyester film having a printing layer, a second polyester film having a metal deposition layer, and a sealant layer may be provided in this order in order to obtain a packaging material exhibiting a metallic tone. When bonding these polyester films to each other, an adhesive resin layer may be used.In a conventional packaging material, the adhesive resin layer is formed of a material derived from fossil fuel, and the biomass degree of the entire packaging material is determined. Was the cause of the decrease. Therefore, in the packaging material in which the first polyester film having the printing layer, the second polyester film having the metal deposition layer, and the sealant layer are laminated in this order, the biomass degree of the entire packaging material is further increased, and the environmental load is reduced. It is required to reduce it.

  The present invention has been made to solve the above problems. That is, an object of the present invention is to provide a packaging material and a pouch which can reduce the environmental load and exhibit a metallic tone.

The present invention includes the following inventions.
[1] A packaging material in which a first polyester film having a printing layer, a second polyester film having a metal deposition layer, and a sealant layer are laminated in this order, wherein the first polyester film and the second polyester film are provided. A first adhesive resin layer, or an anchor coat layer and a first adhesive resin layer interposed therebetween, wherein the first adhesive resin layer contains low-density polyethylene derived from biomass, and the sealant layer contains polyethylene , Packaging materials.

[2] The packaging material according to [1], wherein the first adhesive resin layer is a low-density polyethylene.

[3] The above-mentioned [1] or [2], wherein the first adhesive resin layer contains at least 50% by mass of biomass-derived low-density polyethylene, and the first adhesive resin layer is adjacent to the metal-deposited layer. ] The packaging material according to [1].

[4] The packaging material according to any one of [1] to [3], wherein the first polyester film contains biomass-derived polyester or recycled polyester.

[5] The packaging material according to any one of [1] to [4], wherein the second polyester film includes biomass-derived polyester or recycled polyester.

[6] The packaging material according to any one of [1] to [5], further including a second adhesive resin layer interposed between the second polyester film and the sealant layer.

[7] The packaging material according to the above [6], wherein the second adhesive resin layer contains low-density polyethylene.

[8] The packaging material according to [7], wherein the low-density polyethylene contained in the second adhesive resin layer includes biomass-derived low-density polyethylene.

[9] The printing layer includes a binder resin and a colorant, the binder resin includes a cured product of a polyol and an isocyanate compound, and at least one of the polyol and the isocyanate compound includes a component derived from biomass. The packaging material according to any one of the above [1] to [8].

[10] A pouch including the packaging material according to any one of [1] to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the environmental load can be reduced and the packaging material and pouch which exhibit a metallic tone can be provided.

It is sectional drawing of the packaging material which concerns on embodiment. It is sectional drawing of another packaging material which concerns on embodiment. It is sectional drawing of another packaging material which concerns on embodiment. It is a front view of the pouch concerning an embodiment.

  Hereinafter, a packaging material and a pouch according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a sectional view of a packaging material according to the present embodiment, FIGS. 2 and 3 are sectional views of other packaging materials according to the present embodiment, and FIG. 3 is a front view of a pouch according to the present embodiment. is there.

<<<< Packaging material >>>>
The packaging material 10-1 shown in FIG. 1 includes a first polyester film 11 having a printing layer 11A, a first adhesive resin layer 12, a second polyester film 13 having a metal deposition layer 13A, and a sealant layer 14. They are provided in this order. The first adhesive resin layer 12 is adjacent to the metal deposition layer 13A. Further, the packaging material 10 includes an anchor coat layer 15 and a second adhesive resin layer 16 interposed between the second polyester film 13 and the sealant layer 14. The anchor coat layer 15 is adjacent to the second polyester film 13.

<<< first polyester film having a printing layer >>
The first polyester film 11 having the print layer 11A has the print layer 11A formed on one surface of the first polyester film 11. The printing layer 11A is joined to the first polyester film 11 without an adhesive layer.

<First polyester film>
The first polyester film 11 is a film containing polyester. The “polyester” in the present specification is obtained by a polycondensation reaction between a diol unit and a dicarboxylic acid unit. Examples of the first polyester film 11 include a film containing polyethylene terephthalate.

  The thickness of the first polyester film 11 is preferably 6 μm or more and 20 μm or less. The lower limit of the thickness of the first polyester film 11 is more preferably 12 μm or more, and the upper limit is more preferably 16 μm or less.

  The first polyester film 11 may be a stretched plastic film stretched in a predetermined direction. In this case, the first polyester film 11 may be a uniaxially stretched film stretched in one predetermined direction or a biaxially stretched film stretched in two predetermined directions. The stretched plastic film is obtained by, for example, heating a plastic film extruded onto a cooling drum by roll heating, infrared heating, or the like, and stretching the plastic film in the longitudinal direction. This stretching is preferably performed by utilizing the peripheral speed difference between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. Further, the magnification of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. If the stretching ratio is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film.

  The longitudinally stretched film is successively subjected to transverse stretching, heat setting, and heat relaxation, in order, to form a biaxially stretched film. The transverse stretching is usually performed in a temperature range of 50 ° C or more and 100 ° C or less. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, though it depends on the required characteristics of the application. If the ratio is less than 2.5 times, the thickness unevenness of the film becomes large and it is difficult to obtain a good film. If the ratio exceeds 5.0 times, breakage tends to occur during film formation.

  The first polyester film 11 may contain various additives as long as its properties are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, release agents, antioxidants, ions Exchange agents, coloring pigments and the like. The additive is preferably added in a range of 5% by mass to 50% by mass, and more preferably in a range of 5% by mass to 20% by mass, based on the whole resin composition.

The breaking strength of the first polyester film 11 is, for example, 5 kg / mm ² or more and 40 kg / mm ² or less in the flow direction (MD) and 5 kg / mm ² or more and 35 kg / mm ² or less in the direction (TD) orthogonal to the flow direction. In addition, the elongation at break is, for example, 50% or more and 350% or less in the flow direction (MD), and 50% or more and 300% or less in a direction (TD direction) orthogonal to the flow direction. Further, the shrinkage when left in a temperature environment of 150 ° C. for 30 minutes is, for example, 0.1% or more and 5% or less.

  The first polyester film does not have to include biomass-derived polyester, or includes polyester obtained by mechanically recycling a polyester resin product (for example, a PET bottle) (hereinafter, referred to as “recycled polyester”). Although it is not necessary, it is preferable to include biomass-derived polyester or recycled polyester from the viewpoint of reducing the environmental load.

(When the first polyester film contains biomass-derived polyester)
The biomass-derived polyester contained in the first polyester film has a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

  The first polyester film 11 may further include, in addition to the biomass-derived polyester, a fossil fuel-derived polyester having fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. Since the first polyester film 11 contains the biomass-derived polyester, the amount of the fossil fuel-derived polyester can be reduced as compared with the related art, so that the environmental load can be further reduced.

  When the first polyester film 11 contains biomass polyester, the degree of biomass in the first polyester film 11 is preferably 5% or more. If the degree of biomass in the first polyester film 11 is 5% or more, the amount of polyester derived from fossil fuel can be reduced as compared with the related art, so that the environmental load can be further reduced. The lower limit of the biomass degree in the first polyester film 11 is more preferably 10% or more, and more preferably 15% or more (the larger the numerical value, the more preferable). The upper limit of the biomass degree in the first polyester film 11 is 30% or less. , 25% or less (the smaller the value, the better). The “degree of biomass” in the present specification may be indicated by a value obtained by measuring the content of carbon derived from biomass by radiocarbon (C14) measurement, or may be indicated by a weight ratio of the biomass-derived component.

When the value obtained by measuring the content of carbon derived from biomass by radioactive carbon (C14) measurement is indicated as "biomass degree", the "biomass degree" can be obtained as follows. That is, since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), plants that take in carbon dioxide in the atmosphere and grow, for example, corn, also have a C14 content of about 105.5 pMC. It is known that It is also known that C14 is hardly contained in fossil fuels. Therefore, by measuring the ratio of C14 contained in all the carbon atoms in the polyester, the ratio of carbon derived from biomass can be calculated. In the present invention, when the content of C14 in the polyester is defined as PC14, the content Pbio of carbon derived from biomass can be determined as follows.
P _bio (%) = P _C14 /105.5×100
Here, pMC is an abbreviation of Percent Modern Carbon.

Taking polyethylene terephthalate, which is a typical polyester, as an example, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. When only biomass-derived carbon is used, the content P _bio of biomass-derived carbon in polyethylene terephthalate is 20%. On the other hand, the content of biomass-derived carbon in fossil fuel-derived polyethylene terephthalate produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the content of fossil fuel-derived polyethylene terephthalate is The biomass degree is 0%.

  When the “biomass degree” is represented by the weight ratio of the biomass-derived component, the “biomass degree” can be determined as follows. For example, taking polyethylene terephthalate as an example, polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1: 1 as described above. When only the biomass-derived glycol is used as the glycol, the weight ratio of the biomass-derived component in the polyester is about 30%, so that the biomass degree is about 30%. The weight ratio of the biomass-derived component in the fossil fuel-derived polyester produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the biomass degree of the fossil fuel-derived polyester is 0%. Hereinafter, unless otherwise specified, the “degree of biomass” indicates a weight ratio of a biomass-derived component.

  The diol unit of the biomass-derived polyester uses biomass-derived ethylene glycol. This ethylene glycol derived from biomass is obtained from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, for example, by producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used. For example, biomass ethylene glycol commercially available from Indiaglycol Co., Ltd. can be suitably used.

  As the dicarboxylic acid unit of the polyester derived from biomass, a dicarboxylic acid derived from fossil fuel is used. As the dicarboxylic acid, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the derivative of the aromatic dicarboxylic acid include lower alkyl esters of the aromatic dicarboxylic acid, specifically, methyl ester, ethyl ester, propyl ester and butyl. Esters and the like. Of these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as the derivative of the aromatic dicarboxylic acid.

  As the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecane diacid, dimer acid, cyclohexanedicarboxylic acid, and the like, usually have 2 to 40 carbon atoms. And a linear or alicyclic dicarboxylic acid. Further, as the derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as a methyl ester, an ethyl ester, a propyl ester and a butyl ester of the aliphatic dicarboxylic acid or a cyclic acid anhydride of the aliphatic dicarboxylic acid such as succinic anhydride is mentioned. No. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and those containing succinic acid as a main component are particularly preferable. As the derivative of the aliphatic dicarboxylic acid, a methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable. These dicarboxylic acids can be used alone or in combination of two or more.

  The biomass-derived polyester may be a copolymer polyester obtained by adding a copolymer component as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol for forming a crosslinked structure, a trifunctional or higher polycarboxylic acid and / or an anhydride thereof, and a trifunctional carboxylic acid. At least one kind of polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids is exemplified. Among these copolymer components, copolymerized polyesters having a high degree of polymerization tend to be easily produced, and therefore oxycarboxylic acids having a bifunctionality and / or a trifunctionality or more are particularly preferably used. Among them, the use of tri- or higher functional oxycarboxylic acids is most preferable because a polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

  The biomass-derived polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, a general method of melt polymerization, such as performing an esterification reaction and / or a transesterification reaction between the dicarboxylic acid component and the diol component and then performing a polycondensation reaction under reduced pressure, or an organic solvent Can be produced by a known solution heat dehydration condensation method using The amount of the diol used in producing the biomass-derived polyester is substantially equimolar to 100 mol of the dicarboxylic acid or a derivative thereof, but is generally esterification and / or transesterification and / or condensation. Since there is distillation during the polymerization reaction, it is preferable to use an excess of 0.1 mol% or more and 20 mol% or less.

  Forming the first polyester film 11 by using a resin composition of a biomass-derived polyester or a resin composition containing a biomass-derived polyester and a fossil fuel-derived polyester, for example, by a T-die method. Can be. Specifically, after drying the above-described resin composition, the resin composition is supplied to a melt extruder heated to a temperature of not less than the melting point Tm of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition. The first polyester film 11 can be formed by extruding into a sheet shape from a die such as a T-die, and rapidly solidifying the extruded sheet material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

(When the first polyester film contains recycled polyester)
The recycled polyester contained in the first polyester film 11 has ethylene glycol as a diol unit and dicarboxylic acid as a dicarboxylic acid unit, and is obtained by mechanically recycling a polyester resin product. Here, mechanical recycling generally means that a collected polyester resin product such as a PET bottle is crushed and washed with alkali to remove dirt and foreign matter on the surface of the polyester resin product, and then dried at a high temperature and a reduced pressure for a certain period of time. In this method, contaminants remaining inside the polyester are diffused to perform decontamination, remove stains from the polyester resin product, and return to the polyester again.

  The first polyester film 11 may further include non-recycled polyester (hereinafter, referred to as “virgin polyester”) in addition to the recycled polyester. Since the first polyester film 11 contains recycled polyester, the amount of fossil fuel-derived polyester can be reduced as compared with the related art, so that the environmental load can be further reduced. The first polyester film 11 preferably contains recycled polyester at a ratio of 50% by weight or more and 95% by weight or less. Recycled polyester includes recycled polyethylene terephthalate, and virgin polyester includes virgin polyethylene terephthalate.

  When the first polyester film 11 is molded by mixing the recycled polyester and the virgin polyester, there are a method of supplying the first polyester film 11 to a molding machine separately, a method of supplying the mixture after dry blending or the like, and the like. Above all, a method of mixing by dry blending is preferred from the viewpoint of easy operation.

  The first polyester film 11 can be formed by using a resin composition of recycled polyester or a resin composition containing recycled polyester and virgin polyester to form a film by, for example, a T-die method. Specifically, after drying the above-described resin composition, the resin composition is supplied to a melt extruder heated to a temperature of not less than the melting point Tm of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition. The first polyester film 11 can be formed by extruding into a sheet shape from a die such as a T-die, and rapidly solidifying the extruded sheet material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

  The first polyester film 11 composed of such recycled polyester may be a single layer or a multilayer.

<Print layer>
The printing layer 11A is a layer formed by printing for decoration, display of contents, display of a best-before period, display of a manufacturer, a seller, and the like, and display and aesthetics. The printing layer 11A includes, for example, a picture layer for forming a desired arbitrary picture such as a picture, a photograph, a character, a number, a figure, a symbol, and a pattern. The printing layer may further include a ground color layer formed by printing so as to make the picture of the picture layer stand out.

  The printing layer 11A contains a binder resin and a coloring agent. The binder resin contains a cured product of a polyol and an isocyanate compound. The printed layer 11A may not contain a biomass-derived component, but preferably contains a biomass-derived component from the viewpoint of reducing environmental load. Specifically, the binder resin of the printing layer 11A is preferably formed using a cured product in which at least one of a polyol as a main component and an isocyanate compound as a curing agent contains a biomass-derived 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 the polyfunctional alcohol and the polyfunctional carboxylic acid contains a biomass-derived component. The following examples can be given as polyester polyols containing biomass-derived components.
・ Reacted product of polyfunctional alcohol derived from biomass and polyfunctional carboxylic acid derived from biomass ・ Reacted product of polyfunctional alcohol derived from fossil fuel and polyfunctional carboxylic acid derived from biomass ・ Polyfunctional alcohol derived from biomass and derived from fossil fuel With polyfunctional carboxylic acid

  As the polyfunctional alcohol derived from biomass, an aliphatic polyfunctional alcohol obtained from a plant material such as corn, sugar cane, cassava, and sago palm can be used. Examples of the aliphatic polyfunctional alcohols derived from biomass include, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant raw materials by the following method. Glycol (BG), hexamethylene glycol, etc., 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 materials. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the above fermentation method can provide useful by-products such as lactic acid from the viewpoint of safety, and can also keep production costs low. It is also preferred that it is possible.

  Butylene glycol derived from biomass can be produced by producing succinic acid by producing and fermenting glycol from plant raw materials 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 two or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, as the polyfunctional alcohol derived from fossil fuel, there is no particular limitation, 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 include recyclable plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, castor oil, and waste edible oil mainly composed of them. An aliphatic polyfunctional carboxylic acid obtained from a plant material such as oil can be used. Examples of the aliphatic polyfunctional carboxylic acid derived from biomass include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, dimer acid and the like. For example, sebacic acid is produced as a by-product of heptyl alcohol by subjecting ricinoleic acid obtained from castor oil to alkaline pyrolysis. In the present invention, it is particularly preferable to use succinic acid derived from biomass or sebacic acid derived from biomass. These may be used alone or in combination of two or more.

  As the polyfunctional carboxylic acid derived from the fossil fuel, an aliphatic polyfunctional carboxylic acid or an aromatic polyfunctional carboxylic acid can be used. As the aliphatic polyfunctional carboxylic acid derived from fossil fuel, there is no particular limitation, and conventionally known ones can be used. Examples thereof include adipic acid, dodecane diacid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and maleic anhydride. Acids, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, and dimer acid, and ester compounds thereof. 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, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, And pyromellitic acid, and ester compounds thereof. 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 the polyfunctional alcohol and the polyfunctional isocyanate contains a biomass-derived component. The following examples can be given as polyether polyols containing components derived from biomass.
・ Reacted product of polyfunctional alcohol derived from biomass and polyfunctional isocyanate derived from biomass ・ Reacted product of polyfunctional alcohol derived from fossil fuel and polyfunctional isocyanate derived from biomass ・ Multifunctional alcohol derived from biomass and polyfunctional isocyanate 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 biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. The obtained one can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Examples of the biomass-derived diisocyanate include dimer acid diisocyanate (DDI), octamethylene diisocyanate, and decamethylene diisocyanate. Alternatively, a plant-derived diisocyanate can be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by subjecting a carboxyl group of lysine to methyl esterification and then converting an amino group to an isocyanate group. In addition, 1,5-pentamethylene diisocyanate is obtained by decarboxylating a carboxyl group of lysine and then converting an amino group to an isocyanate group.

  Other methods for synthesizing 1,5-pentamethylene diisocyanate include a phosgenation method and a carbamate method. More specifically, the phosgenation method is a method in which 1,5-pentamethylenediamine or a salt thereof is directly reacted with phosgene or a method in which pentamethylenediamine hydrochloride is suspended in an inert solvent and reacted with phosgene. According to the method, 1,5-pentamethylene diisocyanate is synthesized. In the carbamate method, 1,5-pentamethylene diisocyanate or a salt thereof is first carbamate to produce pentamethylene dicarbamate (PDC), and then thermally decomposed to give 1,5-pentamethylene diisocyanate. It is to be synthesized. In the present invention, as a polyisocyanate suitably used, 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: Stabio (registered trademark)) manufactured by Mitsui Chemicals, Inc. may be mentioned.

  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-isocyanate 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), Julilylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4'-diisocyanate diisocyanate Aromatic diisocyanate such as Njiru the like.

  Aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalenediisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as hydrogenated MDI and hydrogenated XDI. 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 print layer 11A contains a biomass-derived component, the biomass degree of the print layer 11A is preferably 5% or more. If the biomass degree of the printed layer 11A is 5% or more, the amount of fossil fuel used can be reduced, and the environmental load can be further reduced. The lower limit of the biomass degree of the print layer 11A is preferably 5% or more and 10% or more (the larger the numerical value, the better), and the upper limit is preferably 50% or less.

The weight of the printed layer 11 after drying is preferably 0.1 g / m ² or more and 10 g / m ² or less. The lower limit of the weight of the printed layer 11 after drying is more preferably 1 g / m ² or more, and the upper limit is more preferably 5 g / m ² or less and 3 g / m ² or less (the smaller the numerical value, the more preferable). ).

  The print layer 11A preferably has a thickness of 0.1 μm or more and 10 μm or less. The lower limit of the thickness of the print layer 11A is more preferably 1 μm or more, and the upper limit is more preferably 5 μm or less and 3 μm or less (the smaller the numerical value, the better).

<<< first adhesive resin layer >>>
The first adhesive resin layer 12 includes low-density polyethylene derived from biomass (hereinafter, referred to as “biomass low-density polyethylene”). The first adhesive resin layer 12 is preferably a layer made of low-density polyethylene. In this case, the first adhesive resin layer 12 may contain fossil fuel-derived low-density polyethylene in addition to biomass low-density polyethylene. Is preferred. Here, low-density polyethylene is generally obtained by radical polymerization using a monomer containing ethylene under a high pressure of 100 MPa or more and 400 MPa or less without using a catalyst. The linear low-density polyethylene is a polyethylene obtained by polymerization of ethylene and an α-olefin under a low pressure of normal pressure to 1 MPa using a transition metal catalyst such as a Ziegler catalyst or a metallocene catalyst. Low-density polyethylene is different from linear low-density polyethylene or high-density polyethylene because polyethylene is a polyethylene that is polymerized under a low pressure of normal pressure to 1 MPa using a transition metal catalyst such as a Ziegler catalyst or a metallocene catalyst. Things.

  The first adhesive resin layer 12 is composed of 5% to 100% by mass of biomass-derived low-density polyethylene and 0% to 95% by mass of fossil fuel-derived low-density fuel based on the entire first adhesive resin layer 12. Polyethylene and 5% to less than 100% by weight of biomass-derived low-density polyethylene and 0% to 95% by weight of fossil fuel-derived low-density polyethylene, and 25% to 75% by weight. It may include a low-density polyethylene derived from biomass of up to 25% by mass and a fossil fuel-derived low-density polyethylene of from 25% to 75% by mass. However, the first adhesive resin layer 12 preferably contains at least 50% by mass of biomass-derived low-density polyethylene based on the entire first adhesive resin layer 12 from the viewpoint of effectively reducing the environmental load.

  The degree of biomass in the 12 first adhesive resin layers is preferably 5% or more. If the degree of biomass in the first adhesive resin layer 12 is 5% or more, the amount of fossil fuel used can be reduced, and the environmental load can be further reduced. The lower limit of the biomass degree of the first adhesive resin layer 12 is preferably 5% or more, 10% or more, 15% or more, and 20% or more (the larger the numerical value, the better). The degree of biomass in the first adhesive resin layer 12 does not need to be 100%. This is because if a biomass-derived raw material is used for a part of the packaging material 10, the purpose of the present invention is to reduce the amount of fossil fuel used compared to the related art.

Density of the first adhesive resin layer 12 is preferably less 0.91 g / cm ³ or more 0.93 g / cm ^3. If the density of the first adhesive resin layer 12 is within the above range, processing and molding can be facilitated. The lower limit of the density of the first adhesive resin layer 12, 0.911 g / cm ³ or more, more preferably 0.915 g / cm ³ or more (the larger the numerical preferred), the upper limit is, 0.928 g / cm ³ Hereinafter, it is more preferable that it is 0.925 g / cm ³ or less (the smaller the numerical value, the better). The density of the first adhesive resin layer 12 is a value measured according to the method specified in the method A in JIS K7112: 1980 after performing the annealing described in JIS K6760: 1995.

  The thickness of the first adhesive resin layer 12 is preferably 5 μm or more and 100 μm or less. When the thickness of the first adhesive resin layer 12 is within the above range, the function of bonding the two layers can be sufficiently achieved. The lower limit of the first adhesive resin layer 12 is more preferably 10 μm or more and 15 μm or more (the larger the numerical value is preferable), and the upper limit is more preferably 60 μm or less and 40 μm or less (the smaller the numerical value is more preferable). .

(Low density polyethylene derived from biomass)
Biomass-derived low-density polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. The monomer that is a raw material of biomass-derived low-density polyethylene may further include a fossil fuel-derived ethylene monomer in addition to a biomass-derived ethylene-containing monomer.

  In general, low-density polyethylene can be obtained by radical polymerization under high pressure of 100 MPa or more and 400 MPa or less using a monomer containing ethylene without using a catalyst. The linear low-density polyethylene is a polyethylene obtained by polymerization of ethylene and an α-olefin under a low pressure of normal pressure to 1 MPa using a transition metal catalyst such as a Ziegler catalyst or a metallocene catalyst. Low-density polyethylene is different from linear low-density polyethylene or high-density polyethylene because polyethylene is a polyethylene that is polymerized under a low pressure of normal pressure to 1 MPa using a transition metal catalyst such as a Ziegler catalyst or a metallocene catalyst. Things.

Density of the low density polyethylene from biomass is preferably less 0.91 g / cm ³ or more 0.93 g / cm ^3. If the density of the biomass low-density polyethylene is 0.91 g / cm ³ or more, the rigidity of the first adhesive resin layer 12 containing the biomass low-density polyethylene can be increased. When the density of the biomass low-density polyethylene is 0.93 g / cm ³ or less, the transparency and mechanical strength of the first adhesive resin layer 12 containing the biomass low-density polyethylene can be increased. The lower limit of the density of the low density polyethylene from biomass, 0.912 g / cm ³ or more, more preferably 0.915 g / cm ³ or more (the larger the numerical preferred), the upper limit is, 0.928 g / cm ³ Hereinafter, it is more preferable that it is 0.925 g / cm ³ or less (the smaller the numerical value, the better). The density of biomass low-density polyethylene is a value measured according to the method specified in Method A of JIS K7112: 1980 after annealing described in JIS K6760: 1995.

  The biomass low-density polyethylene preferably has a melt flow rate (MFR) of 0.1 g / 10 min or more and 10 g / 10 min or less. If the MFR of the biomass low-density polyethylene is 0.1 g / 10 min or more, the extrusion load during molding can be reduced. If the MFR of the biomass low-density polyethylene is 10 g / 10 minutes or less, the mechanical strength of the first adhesive resin layer 12 containing the biomass low-density polyethylene can be increased. The MFR of the biomass low-density polyethylene is more preferably 0.2 g / 10 min or more and 1 g / 10 min or more (the larger the numerical value, the better), and the upper limit is 9 g / 10 min or less, 8.5 g / 10 min. The following is more preferable (the smaller the numerical value, the better). The melt flow rate is a value measured by the method A at a temperature of 190 ° C. and a load of 21.18 N in a method specified in JIS K7210: 1995.

Examples of the biomass-derived low-density polyethylene include biomass-derived low-density polyethylene (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree 95%, manufactured by Braskem). ), Low density polyethylene derived from biomass (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree 95%) manufactured by Braskem.

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

  Various additives may be added to the first adhesive resin layer 12 in addition to the low-density polyethylene as the main component, as long as the properties are not impaired. Examples of additives include a plasticizer, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a slip agent, a release agent, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added. These additives are added in an amount of preferably 1% by mass or more and 20% by mass or less, preferably 1% by mass or more and 10% by mass or less based on the whole low-density polyethylene.

<<< second polyester film having a metal vapor deposition layer >>
The second polyester film 13 having the metal deposition layer 13A has a metal deposition layer 13A formed on one surface of the second polyester film 13.

<Second polyester film>
The second polyester film 13 is a film made of polyester. The second polyester film may not contain the biomass-derived polyester or may not contain the recycled polyester, but preferably contains the biomass-derived polyester or the recycled polyester from the viewpoint of reducing the environmental load.

  When the second polyester film 13 includes a biomass-derived polyester, the second polyester film 13 may further include a fossil fuel-derived polyester in addition to the biomass-derived polyester. Since the second polyester film 13 contains the biomass-derived polyester, the amount of the fossil fuel-derived polyester can be reduced as compared with the related art, so that the environmental load can be further reduced.

  When the second polyester film 13 contains recycled polyester, it may further contain virgin polyester in addition to the recycled polyester. When the second polyester film 13 contains recycled polyester, the amount of fossil fuel-derived polyester can be reduced as compared with the conventional case, so that the environmental load can be further reduced.

  The other description of the second polyester film 13 is the same as that of the first polyester film 11, and the description is omitted here.

<Metal deposition layer>
The metal deposition layer 13A is a deposition layer made of a metal or an alloy thereof. The metal deposition layer 13A can be formed by a conventionally known deposition method using a conventionally known metal. The packaging material may have two or more metal deposition layers. When there are two or more metal deposition layers 13A, each may have the same composition or different compositions.

  As the metal deposition layer 13, for example, aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), titanium (Ti), lead (Pb), A vapor-deposited layer of a metal such as zirconium (Zr) or yttrium (Y), or an alloy thereof can be used.

  The thickness of the metal vapor deposition layer 13 varies depending on the type of metal to be used and the like, but it is desirable to form the metal vapor deposition layer 13 by arbitrarily selecting it within the range of 50 ° to 2000 °, preferably, 100 ° to 1000 °. More specifically, when the deposited layer is an aluminum deposited layer, the thickness of the deposited layer is preferably from 50 to 600, more preferably from 100 to 450.

  The metal deposition layer 13A is formed on the second polyester film 13 by, for example, a physical vapor deposition method (PVD method) such as a vacuum deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method. It is formed by a chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a growth method, a thermal chemical vapor deposition method, and a photochemical vapor deposition method.

<< Sealant layer >>
The sealant layer 14 includes polyethylene. The sealant layer is not particularly limited as long as it contains polyethylene. For example, the sealant layer contains biomass-derived linear low-density polyethylene (LLDPE) and low-density polyethylene (LDPE). It may further include a linear low density polyethylene. Further, the low-density polyethylene contained in the sealant layer 14 may be derived from biomass or may be derived from fossil fuel. By including both biomass-derived linear low-density polyethylene and low-density polyethylene, the sealant layer 14 can achieve both excellent impact resistance and excellent tearability when a pouch is manufactured. Linear low-density polyethylene has many short molecular chains in the molecular chain and is excellent in sealing performance.

  The content of the low-density polyethylene in the sealant layer 14 (the total content when two types derived from biomass and fossil fuel are included) is preferably 5% by mass or more and 25% by mass or less, more preferably 10% by mass or more. 20 mass% or less. Further, the content of the biomass-derived and / or fossil fuel-derived linear low-density polyethylene in the sealant layer (the total content when two types are included) is preferably 75% by mass or more and 95% by mass or less. Preferably it is 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 14, it is possible to achieve both excellent impact resistance and excellent hand-cutting properties when a pouch is manufactured.

  The biomass degree of the sealant layer 14 is preferably 5% or more and 30% or less. When the biomass degree is in the above range, the amount of fossil fuel used can be reduced while the cost is suppressed, and the environmental load can be further reduced. The lower limit of the biomass degree of the sealant layer 14 is preferably 10% or more and 15% or more (the larger the numerical value, the better), and the upper limit is preferably 25% or less, 20% or less (the larger the numerical value, the better). preferable).

The density of the linear low-density polyethylene and the low-density polyethylene contained in the sealant layer 14 is preferably less than 0.93 g / cm ³ . If the density of the linear low-density polyethylene and the low-density polyethylene is less than 0.93 g / cm ³ , the mechanical strength of the sealant layer 14 can be increased. The lower limit of the density of the linear low-density polyethylene and the low-density polyethylene contained in the sealant layer 14 is 0.91 g / cm ³ or more, 0.912 g / cm ³ or more, from the viewpoint of increasing the rigidity of the sealant layer. more preferably 0.915 g / cm ³ or more (the larger the numerical preferable), the upper limit is, 0.928 g / cm ³ or less, more it is larger and more preferably (number is 0.925 g / cm ³ or less preferable). Note that the MFR of the linear low-density polyethylene may be lower than the MFR of the low-density polyethylene. The densities of the linear low-density polyethylene and the low-density polyethylene are values measured according to the method specified in Method A in JIS K7112: 1980 after annealing described in JIS K6760: 1995.

  The melt flow rate (MFR) of the linear low-density polyethylene and the low-density polyethylene contained in the sealant layer 14 is preferably from 0.1 g / 10 min to 10 g / 10 min. 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 molding can be reduced. When the MFR of the linear low-density polyethylene and the low-density polyethylene is 10 g / 10 minutes or less, the mechanical strength of the sealant layer 14 can be increased. The lower limit of the MFR of the linear low-density polyethylene and the low-density polyethylene contained in the sealant layer 14 is more preferably 0.2 g / 10 min or more and 1 g / 10 min or more (the larger the numerical value, the more preferable), and the upper limit. Is more preferably 9 g / 10 min or less and 8.5 g / 10 min or less (the smaller the numerical value, the better). Note that the MFR of the linear low-density polyethylene may be lower than the MFR of the low-density polyethylene.

Examples of the biomass-derived linear low-density polyethylene used for the sealant layer 14 include biomass-derived linear low-density polyethylene (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1. 0 g / 10 min, biomass degree 87%), biomass-derived linear low-density polyethylene manufactured by Braskem (trade name: SLL318, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min, biomass degree) 87%), biomass-derived linear low-density polyethylene (trade name: SLH218, density: 0.916 g / cm ³ , MFR: 2.3 g / 10 min, biomass degree 87%) manufactured by Braskem. .

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

  The thickness of the sealant layer 14 is preferably 80 μm or more and 150 μm or less. When the thickness of the sealant layer is within the above range, excellent impact resistance and excellent tearability can be achieved at the time of manufacturing the pouch. The lower limit of the thickness of the sealant layer 14 is preferably 90 μm or more and 100 μm or more (the larger the value, the better), and the upper limit is preferably 140 μm or less, 130 μm or less (the smaller the value, the better).

<< Anchor coat layer >>
The anchor coat layer 15 is provided between the second polyester film 13 and the second adhesive resin layer 16. Thereby, the adhesion strength between the second polyester film 13 and the second adhesive resin layer 16 can be increased, and the occurrence of delamination after hot water sterilization can be prevented.

  Examples of the anchor coating agent include any resin having a heat-resistant temperature of 135 ° C. or higher, such as a vinyl-modified resin, an epoxy resin, a urethane resin, and a polyester resin. An anchor coating agent composed of a polyacrylic or polymethacrylic resin having a hydroxyl group and an isocyanate compound as a curing agent can be preferably used. Further, a silane coupling agent may be used as an additive thereto, and nitrified cotton may be used in combination to increase heat resistance.

  The anchor coat layer is coated with the above-mentioned anchor coat agent by a known coating method such as a roll coat, a gravure coat, a knife coat, a dip coat, a spray coat, and the solvent, a diluent and the like are dried and removed, and cured. By doing so, it can be formed. The thickness of the anchor coat layer is preferably from 0.2 μm to 0.3 μm.

<< second adhesive resin layer >>
The second adhesive resin layer 16 contains low-density polyethylene. The low-density polyethylene contained in the second adhesive resin layer 16 may be a fossil fuel low-density polyethylene, but preferably contains biomass low-density polyethylene from the viewpoint of reducing environmental load. When the low-density polyethylene included in the second adhesive resin layer 16 includes biomass low-density polyethylene, the low-density polyethylene may further include fossil fuel low-density polyethylene.

  The other description of the second adhesive resin layer 16 is the same as that of the first adhesive resin layer 12, and the description is omitted here.

<<<< Production method of packaging material >>>>
Using a sand lamination method, the packaging material 10-1 includes a first polyester film 11 having a printing layer 11A and a second polyester film 13 having a metal deposition layer 13A via a first adhesive resin layer 12 which is melt-extruded. It can be obtained by bonding the second polyester film 13 having the metal deposition layer 13A and the sealant layer 14 via the bonded and melt-extruded second adhesive resin layer 16.

<<<< Other packaging materials >>
The packaging material 10-1 shown in FIG. 1 does not have an anchor coat layer between the first polyester film 11 and the first adhesive resin layer 12, but is similar to the packaging material 10-2 shown in FIG. Further, an anchor coat layer 17 may be provided between the first polyester film 11 and the first adhesive resin layer 12. The anchor coat layer 17 is the same as the anchor coat layer 15 and will not be described here. In FIGS. 2 and 3, the layers denoted by the same reference numerals as those in FIG. 1 are the same as the layers shown in FIG.

  Although the packaging material 10-1 shown in FIG. 1 includes the anchor coat layer 15 and the second adhesive resin layer 16, as in the packaging material 10-3 shown in FIG. The resin layer need not be provided. In the packaging material 10-3, the sealant layer 14 is bonded to the second polyester film 13.

  According to the present embodiment, the first adhesive resin layer 12 interposed between the first polyester film 11 having the printing layer 11A and the second polyester film 13 having the metal deposition layer 13A contains biomass low-density polyethylene. Therefore, the amount of fossil fuel polyethylene can be reduced as compared with the conventional case. Thereby, the environmental load can be reduced and the packaging materials 10-1, 10-2, and 10-3 exhibiting a metallic tone can be obtained.

  When comparing a metal foil such as an aluminum foil with a polyester film having a metal deposition layer, the polyester film has higher rigidity than the metal foil, and therefore, the polyester film having the metal deposition layer is compared with a metal foil such as an aluminum foil. The piercing strength and waist can be improved, and it is harder to cut than a metal foil such as an aluminum foil, so that the sealing strength can be improved. On the other hand, when a polyester film having a metal vapor-deposited layer is used, the tearability may be lower than that of a metal foil such as an aluminum foil. In the present embodiment, the second polyester film 13 having the metal deposition layer 13A is used, and the second polyester film 13 having the metal deposition layer 13A is formed of a layer containing polyethylene having a good tear property (a layer containing low-density polyethylene). By sandwiching between the first adhesive resin layer 12 and the second adhesive resin layer 16 containing low-density polyethylene and the sealant layer 14 containing polyethylene, it is possible to improve the piercing strength, waist and seal strength while ensuring tearability. it can.

<<<< Pouch >>>>
Hereinafter, a pouch including the packaging material 10-1 will be described. Although a pouch including the packaging material 10-1 will be described with reference to FIG. 4, a packaging material 10-2 or a packaging material 10-3 may be provided instead of the packaging material 10-1.

  The pouch 20 shown in FIG. 4 has a storage space for storing contents. The contents are not particularly limited, but include, for example, foods and seasonings. However, the contents are not limited to these.

  The pouch 20 has a front film 21 and a back film 22 as shown in FIG. In the pouch 20, the front face film 21 and the back face film 22 are made of a packaging material 10-1. However, it is sufficient that the packaging material 10-1 and the like are used for at least a part of the pouch 20, and it is not necessary to use the packaging material for the whole. The front film 21 and the back film 22 made of the packaging material 10-1 are arranged such that the sealant layer 41 is inside the pouch 20.

  The pouch 20 includes a first edge 20A, a second edge 20B parallel to the first edge 20A, a third edge 20C extending between the first edge 20A and the second edge 20B, and a third edge 20C parallel to the third edge 20C. And four edges 20D.

  The pouch 20 includes a first end seal portion 23 formed on the second edge 20B side, a second end seal portion 24 formed on the third edge 20C side, and a third end formed on the fourth edge 20D side. An external seal portion 25 is provided. In FIG. 4, the first edge 20A side of the pouch 20 is open, but after the contents are filled in the accommodation space, the pouch 20 is heat-sealed, and the fourth edge surrounded by the two-dot chain line with the first edge 20A. A fourth end seal portion is formed in the seal portion forming region R, and the pouch 20 is sealed.

  The first end seal portion 23, the second end seal portion 24, and the third end seal portion 25 are portions where the front film 21 and the back film 22 are joined to each other at each end. The first end seal portion 23, the second end seal portion 24, and the third end seal portion 25 are formed by heat sealing the front film 21 and the back film 22.

  The second end seal portion 24 and the third end seal portion 25 are provided with opening start means 26 such as a notch or a notch at an opening position to facilitate opening.

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
<Example 1>
As the first polyester film, a biaxially stretched 12 μm thick PET film 1 containing a biomass-derived component was prepared. Subsequently, a printed layer was formed on the corona-treated surface of the PET film 1 using an ink containing a biomass-derived component. In the step of forming the print layer, first, a polyester polyol, which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from a fossil fuel, was prepared as a main agent. Further, an isocyanate compound derived from a fossil fuel was prepared as a curing agent. Subsequently, a colorant was added to a cured product of a polyester polyol containing a biomass-derived component and an isocyanate compound derived from a fossil fuel to obtain an ink. Subsequently, an ink was applied to one surface of the PET film 1 in a predetermined pattern to form a print layer. Thus, a PET film 1 having a print layer was obtained.

  In addition, a biaxially stretched PET film 2 having a thickness of 12 μm and containing a biomass-derived component was prepared as a second polyester film. Subsequently, aluminum (Al) was deposited on the corona-treated surface of the PET film 2 by a vacuum deposition method to form an Al deposited layer having a thickness of 400 °. Thus, a PET film 2 having an Al deposition layer was obtained.

Further, 60 parts by mass of a linear low-density polyethylene derived from fossil fuel (density: 0.918 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree: 0%) and a low-density polyethylene derived from fossil fuel ( Density: 0.924 g / cm ³ , MFR: 2.0 g / 10 min, biomass degree: 0%) 20 parts by mass, and biomass-derived linear low-density polyethylene (LLDPE, manufactured by Braskem Co., trade name: SLL118, (Density: 0.916 g / cm ³ , MFR: 1.0 g / 10 min, biomass degree: 87%) and 20 parts by mass were melt-kneaded to obtain a resin composition. Next, the obtained resin composition was formed into a film by a top-blowing air-cooled inflation co-extrusion film-forming machine to obtain a polyethylene film 1 (biomass degree: 17.4%) having a thickness of 130 μm as a sealant layer.

On the surface of the printing layer in the PET film 1 having the printing layer, a low-density polyethylene derived from biomass (LDPE, manufactured by Braskem, trade name: SBC818, density: 0.918 g / cm ³ , MFR: While extruding 8.1 g / 10 min, biomass degree: 95%), a 15 μm-thick low-density polyethylene layer 1 (biomass degree: 95%) as a first adhesive resin layer made of this biomass-derived low-density polyethylene was added. Then, the PET film 2 having the Al vapor-deposited layer was bonded so that the Al vapor-deposited layer was in contact with the low-density polyethylene layer.

  Next, the surface of the PET film 2 having the Al vapor-deposited layer opposite to the Al vapor-deposited layer is coated with a two-component curable anchor coat agent (A3210 / A3075, manufactured by Mitsui Chemicals, Inc., polyurethane type) to form an anchor coat layer. Formed.

Thereafter, on the anchor coat layer, a low density polyethylene derived from biomass (LDPE, manufactured by Braskem, trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min.) While extruding a biomass degree of 95%), the polyethylene film 1 was passed through a low-density polyethylene layer 2 (biomass degree: 95%) having a thickness of 15 μm as a second adhesive resin layer made of this biomass-derived low-density polyethylene. Were pasted together. Thus, PET film 1 (bio) / printed layer (bio) / low density polyethylene layer 1 (bio) / Al deposited layer / PET film 2 (bio) / anchor coat layer / low density polyethylene layer 2 (bio) / polyethylene A packaging material in which the film 1 (bio) was laminated in this order was obtained. In addition, “/” was used as a notation indicating a boundary between layers when listing the layers, and “(bio)” was used as a notation including a biomass-derived component.

<Example 2>
In Example 2, instead of the PET film 2 having the Al vapor-deposited layer, a fossil fuel-derived PET film 3 (1310, 12 μm thick, manufactured by Toray Film Processing Co., Ltd.) on which an aluminum vapor-deposited layer was formed was used. Except for the above, a packaging material was obtained in the same manner as in Example 1. The packaging material according to Example 2 is PET film 1 (bio) / printed layer (bio) / low density polyethylene layer 1 (bio) / Al deposited layer / PET film 3 / anchor coat layer / low density polyethylene 2 (bio) / Polyethylene film 1 (bio) was laminated in this order.

<Example 3>
In Example 3, instead of the low-density polyethylene layer 1 as the first adhesive resin layer, low-density polyethylene derived from biomass (LDPE, manufactured by Braskem, trade name: SBC818, density: 0.918 g / cm ³ , MFR) : 8.1 g / 10 min, biomass degree: 95%) 50 parts by mass and low-density polyethylene derived from fossil fuel (density: 0.924 g / cm ³ , MFR: 2.0 g / 10 min, biomass degree: 0%) A packaging material was obtained in the same manner as in Example 1, except that the low-density polyethylene layer 3 was formed by extruding the resin composition containing 50 parts by mass. The packaging material according to Example 3 is PET film 1 (bio) / printed layer (bio) / low density polyethylene layer 3 (bio) / Al deposited layer / PET film 2 / anchor coat layer / low density polyethylene 2 (bio) / Polyethylene film 1 (bio) was laminated in this order.

<Example 4>
In Example 4, in place of the PET film 2 having the Al vapor-deposited layer, a PET film 3 (1310, 12 μm thick, manufactured by Toray Film Processing Co., Ltd.) derived from a fossil fuel having an aluminum vapor-deposited layer was used. Except for the above, a packaging material was obtained in the same manner as in Example 3. The packaging material according to Example 4 is PET film 1 (bio) / printed layer (bio) / low density polyethylene layer 3 (bio) / Al deposited layer / PET film 3 / anchor coat layer / low density polyethylene 2 (bio) / Polyethylene film 1 (bio) was laminated in this order.

<Example 5>
In Example 5, a 12 μm-thick recycled PET film 1 was used instead of the PET film 1, and a 12 μm-thick recycled PET film 2 was used instead of the PET film 2, in the same manner as in Example 1. To obtain the packaging material. The recycled PET film 1 and the recycled PET film 2 were obtained by mechanically recycling a PET bottle. The packaging material according to Example 5 is composed of recycled PET film 1 / printed layer (bio) / low density polyethylene layer 1 (bio) / Al deposited layer / recycled PET film 2 / anchor coat layer / low density polyethylene 2 (bio) / Polyethylene film 1 (bio) was laminated in this order.

<Example 6>

  In Example 6, a fossil fuel-derived PET film 3 (Toray Film Processing Co., Ltd., 1310, thickness 12 μm) having an aluminum vapor-deposited layer was used instead of the recycled PET film 2 having an Al vapor-deposited layer. Except for the above, a packaging material was obtained in the same manner as in Example 5. The packaging material according to Example 6 is a recycled PET film 1 / printed layer (bio) / low density polyethylene layer 1 (bio) / Al deposited layer / PET film 3 / anchor coat layer / low density polyethylene 2 (bio) / polyethylene. Film 1 (bio) was laminated in this order.

10-1, 10-2, 10-3 Packaging material 11 First polyester film 11A Printing layer 12 First adhesive resin layer 13 Second polyester film 13A Metal deposition layer 14 Sealant layer 15 Anchor coat Layer 16: Second adhesive resin layer

Claims (10)

A packaging material obtained by laminating a first polyester film having a printing layer, a second polyester film having a metal deposition layer, and a sealant layer in this order,
A first adhesive resin layer interposed between the first polyester film and the second polyester film, or an anchor coat layer and a first adhesive resin layer,
The first adhesive resin layer contains low-density polyethylene derived from biomass,
A packaging material, wherein the sealant layer contains polyethylene.   The packaging material according to claim 1, wherein the first adhesive resin layer is a low-density polyethylene.   The packaging material according to claim 1 or 2, wherein the first adhesive resin layer contains 50% by mass or more of biomass-derived low-density polyethylene, and the first adhesive resin layer is adjacent to the metal-deposited layer. .   The packaging material according to any one of claims 1 to 3, wherein the first polyester film includes biomass-derived polyester or recycled polyester.   The packaging material according to any one of claims 1 to 4, wherein the second polyester film includes biomass-derived polyester or recycled polyester.   The packaging material according to any one of claims 1 to 5, further comprising a second adhesive resin layer interposed between the second polyester film and the sealant layer.   The packaging material according to claim 6, wherein the second adhesive resin layer contains low-density polyethylene.   The packaging material according to claim 7, wherein the low-density polyethylene contained in the second adhesive resin layer includes biomass-derived low-density polyethylene.   The printing layer contains a binder resin and a colorant, the binder resin contains a cured product of a polyol and an isocyanate compound, and at least one of the polyol and the isocyanate compound contains a component derived from biomass. 9. The packaging material according to any one of 1 to 8. A pouch comprising the packaging material according to any one of claims 1 to 9.

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