JP7174341B2 - Laminate and packaging bag provided with the same - Google Patents

Description

The present invention relates to a laminate comprising at least a first substrate layer, a barrier layer, a second substrate layer and a sealant layer in this order. Furthermore, it is related with the packaging bag provided with this laminated body.

2. Description of the Related Art Conventionally, various packaging materials have been developed and proposed for filling and packaging various articles such as food and drink, pharmaceuticals, chemicals, cosmetics, and the like. Such packaging materials are required to have various physical properties depending on the purpose of packaging, contents to be filled, storage/distribution of packaged products, and the like. For example, one of their physical properties is a gas barrier property that prevents permeation of oxygen, water vapor, and the like. In addition, impact resistance and hand-tearability when used as packaging bags are also required.

In recent years, along with the increasing demand for building a recycling-based society, the use of biomass has been attracting attention in the field of materials as well as the use of fossil fuels, as is the case with energy. Attempts have been made to employ biomass materials in films such as those described above. For example, Patent Document 1 proposes a laminate using biomass polyester and biomass polyolefin.

JP 2014-133338 A

There is still a need for a packaging material that can achieve both the properties required for packaging materials as described above and the reduction in the amount of fossil fuels used. An object of the present invention is to provide a laminate that can effectively solve such problems.

The present invention provides a laminate comprising at least a first substrate layer, a barrier layer, a second substrate layer, and a sealant layer in this order,
The first base material layer contains polyethylene terephthalate having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit,
The sealant layer is a laminate containing linear low-density polyethylene derived from fossil fuel and low-density polyethylene derived from fossil fuel.

In the laminate according to the present invention, the second substrate layer may contain polyamide or polybutylene terephthalate.

In the laminate according to the present invention, the sealant layer may include biomass-derived linear low-density polyethylene, fossil fuel-derived linear low-density polyethylene, and fossil fuel-derived low-density polyethylene.

In the laminate according to the present invention, the sealant layer may contain 5% by mass or more and 25% by mass or less of low-density polyethylene derived from fossil fuel.

In the laminate according to the present invention, the sealant layer may contain a total of 75% by mass or more and 95% by mass or less of linear low-density polyethylene derived from biomass and linear low-density polyethylene derived from fossil fuel.

In the laminate according to the present invention, the barrier layer may contain a metal foil or a deposited layer of inorganic or inorganic oxide.

The laminate according to the present invention may further include a printed layer between the first substrate layer and the barrier layer.

The present invention is a packaging bag comprising the laminate described above.

ADVANTAGE OF THE INVENTION According to this invention, while having various characteristics required as a packaging material, the laminated body which can reduce an environmental load can be provided.

1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. FIG. 3 is a schematic cross-sectional view showing an example of a second base material layer of a laminate according to the present invention; It is a model front view which shows an example of the packaging bag by this invention. 5 is an A-A' cross-sectional view of the spout portion in the packaging bag of FIG. 4. FIG.

<Laminate>
A laminate according to the present invention includes at least a first substrate layer, a barrier layer, a second substrate layer, and a sealant layer in this order. The laminate may further comprise adhesive layers, printing layers, other layers and the like. When the laminate has two or more adhesive layers and other layers, each layer may have the same composition or different compositions.

A laminate according to the present invention will be described with reference to the drawings. Examples of schematic cross-sectional views of laminates according to the present invention are shown in FIGS. 1 and 2. FIG. The laminate 10 shown in FIG. 1 includes a first substrate layer 11, a barrier layer 12, a second substrate layer 13, and a sealant layer 14 in this order. In the packaging bag including the laminate 10, the sealant layer 13 is positioned on the inner surface side.

The laminate 20 shown in FIG. 2 includes a first base layer 21, a printed layer 25, an adhesive layer 26, a barrier layer 22, a second base layer 23, an adhesive layer 27, and a sealant layer. 24 in this order. The packaging bag including the laminate 20 has the sealant layer 24 located on the inner surface side.

Each layer constituting the laminate will be described below.

[First base material layer]
A laminate according to the present invention comprises at least a first substrate layer. By including the base material layer in the laminate, the strength can be improved when the packaging bag is manufactured.

The first base material layer contains biomass-derived polyethylene terephthalate (hereinafter also referred to as PET). Biomass-derived PET is PET having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit. The base material layer may further contain PET derived from fossil fuel, in which ethylene glycol derived from fossil fuel is used as a diol unit and terephthalic acid derived from fossil fuel is used as a dicarboxylic acid unit. It suffices if the base material layer as a whole can achieve the following biomass degree. In the present invention, since the substrate layer contains biomass-derived PET, the amount of fossil fuel-derived PET can be reduced compared to the conventional case, and the environmental load can be reduced.

In the present invention, the "biomass degree" (biomass-derived carbon concentration) of the substrate layer is a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in PET, the ratio of biomass-derived carbon can be calculated. In the present invention, the biomass-derived carbon content _{Pbio can be obtained as follows, where Pc14} is the content of _C14 in PET.
P _bio (%) = P _C14 /105.5 x 100
Note that PMC is an abbreviation for Percent Modern Carbon.

PET is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1:1. The derived carbon content P _bio is 20%. In the present invention, the content of biomass-derived carbon measured by radioactive carbon (C14) with respect to the total carbon in the biomass-derived PET is preferably 10% or more and 20% or less, and 10% or more and 19%. It may be below. When the content of biomass-derived carbon in biomass-derived PET is 10% or more, it is suitable as a carbon offset material. In addition, the content of biomass-derived carbon in fossil fuel-derived PET produced using fossil fuel-derived ethylene glycol and fossil fuel-derived dicarboxylic acid is 0%, and the biomass degree of fossil fuel-derived PET becomes 0%.

In the present invention, the biomass degree of the substrate layer is 5% or more, preferably 10% or more, and more preferably 15% or more. If the biomass degree of the base material layer is 5% or more, the amount of fossil fuel-derived PET can be reduced compared to the conventional method, and the environmental load can be reduced.

The degree of biomass can be expressed as the content of biomass-derived carbon obtained by measuring radioactive carbon (C14) as described above, and may also be expressed as the weight ratio of biomass-derived components. For example, when the "biomass degree" of the substrate layer is represented by the weight ratio of the biomass-derived component, the "biomass degree" can be obtained as follows. PET is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms at a molar ratio of 1:1. Since the weight ratio of the derived components is about 30%, the degree of biomass is about 30%. In addition, 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%.

When the substrate layer is a stretched PET film, the PET film used for the 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, and preferably in the TD direction. is 150 MPa or more and 300 MPa or less, more preferably 150 MPa or more and 300 MPa or less, and the tensile elongation is preferably 50% or more and 250% or less, more preferably 70% or more and 200% or less in the MD direction, and the TD direction is preferably 50% or more and 250% or less, more preferably 60% or more and 200% or less. Tensile strength and tensile elongation can be measured according to JIS K 7127.

The substrate layer preferably has a thickness of 5 μm to 40 μm, more preferably 8 μm to 25 μm. If the thickness of the base material layer is within the above range, molding is easy, and it can be suitably used as a packaging material.

[Second base material layer]
(First Configuration of Second Base Material Layer)
The second base material layer according to the first configuration is a resin layer containing polyamide such as nylon. The second substrate layer is preferably stretched, more preferably biaxially stretched.

Polyamides 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, which is inferior in water resistance, inside the laminate instead of outside it, the strength required for the packaging bag can be improved without impairing the water resistance.

When the second base layer is a stretched nylon film, the nylon film used for the second base layer has a tensile strength in the MD direction of preferably 150 MPa or more and 350 MPa or less, more preferably 200 MPa or more and 300 MPa or less, TD direction, preferably 150 MPa or more and 400 MPa or less, more preferably 200 MPa or more and 350 MPa or less, and the tensile elongation in the MD direction is preferably 50% or more and 200% or less, more preferably 70% or more and 150% or less. It is preferably 30% or more and 200% or less, more preferably 50% or more and 150% or less in the TD direction.

(Second Configuration of Second Base Layer)
The second base material layer according to the first configuration contains polybutylene terephthalate (hereinafter also referred to as PBT) as a main component. For example, the second base material layer contains 51% by mass or more of PBT.

The content of PBT in the second base material layer according to the second configuration is preferably 51% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 75% by mass or more, and most Preferably, it is 80% by mass or more. By setting the PBT content to 51% by mass or more, the second base material layer can have excellent impact strength and pinhole resistance.

PBT used as a main component preferably contains 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and most preferably 100% terephthalic acid as a dicarboxylic acid component. in mol %. 1,4-Butanediol is preferably 90 mol % or more, more preferably 95 mol % or more, still more preferably 97 mol % or more, and most preferably 1,4-butanediol as a glycol component during polymerization. It does not contain anything other than by-products produced by the ether bond of butanediol.

The second base material layer may contain a polyester resin other than PBT. This makes it possible to adjust the film formability and the mechanical properties of the second base material layer when the film-like base material 1 is biaxially stretched, for example. The amount of the polyester resin other than PBT added is preferably 40% by mass or less.

The film-like second base material layer according to the second configuration can be produced, for example, by a casting method. FIG. 3 is a cross-sectional view showing an example of the layer structure of the second base material layer. When the second base material layer is produced by casting a multilayered resin, the second base material layer consists of a multi-layer structure including a plurality of layers 31, as shown in FIG. Each of the multiple layers 31 contains PBT as a main component. For example, each of the layers 31 contains 51 wt% or more of PBT. In the plurality of layers 31 , the n+1th layer 31 is directly laminated on the nth layer 31 . That is, no adhesive layer or adhesive layer is interposed between the layers 31 . The second base material layer is composed of a multi-layer structure including at least 10 layers or more, preferably 60 layers or more, more preferably 250 layers or more, still more preferably 1000 layers or more. The thickness of layer 31 is preferably 3 nm or more, more preferably 10 nm or more. Also, the thickness of the layer 31 is preferably 200 nm or less, more preferably 100 nm or less.

The thickness of the second base material layer according to the second configuration is preferably 9 μm or more, more preferably 12 μm or more. Also, the thickness of the second base material layer according to the second configuration is preferably 25 μm or less, more preferably 20 μm or less. By setting the thickness of the second base material layer to 9 μm or more, the base material 1 comes to have sufficient strength. Further, by setting the thickness of the second base layer to 25 μm or less, the second base layer exhibits excellent moldability. Therefore, it is possible to efficiently carry out the process of manufacturing the packaging bag by processing the laminate including the second base material layer.

(Third Configuration of Second Base Material Layer)
The second base material layer according to the third configuration contains polyester containing butylene terephthalate as a main repeating unit. For example, the second base material layer is mainly composed of 1,4-butanediol as a glycol component or an ester-forming derivative thereof and terephthalic acid as a dibasic acid component or an ester-forming derivative thereof. Including homo- or copolymer-type polyesters obtained by condensation. The content of PBT in the second base material layer according to the third configuration is preferably 51% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and further preferably 80% by mass or more, Most preferably, it is 90% by mass or more. Moreover, it is preferable that the second base material layer according to the third configuration is composed only of polybutylene terephthalate and an additive.

In order to impart mechanical strength to the second base layer, PBT preferably has a melting point of 200° C. or higher and 250° C. or lower and an IV value of 1.10 dl/g or higher and 1.35 dl/g or lower. . Furthermore, those having a melting point of 215° C. or more and 225° C. or less and an IV value of 1.15 dl/g or more and 1.30 dl/g or less are particularly preferable. These IV values may be met by the entire material that makes up the second substrate layer. IV values can be calculated based on JIS K 7367-5:2000.

The second base material layer according to the third configuration may contain a polyester resin other than PBT, such as PET, in an amount of 30% by mass or less. By including PET in addition to PBT in the second base material layer, crystallization of PBT can be suppressed, and stretchability of the PBT film can be improved.

As a method for producing the film-like second substrate layer according to the third configuration, for example, a biaxial stretching method in which an unstretched original fabric is stretched to obtain a stretched film can be adopted. The biaxial stretching method is not particularly limited. For example, the longitudinal direction and the transverse direction may be stretched simultaneously, or the longitudinal direction and the transverse direction may be successively stretched by a tubular method or a tenter method. Among these methods, the tubular method is particularly preferably employed because it is possible to obtain a stretched film having a good balance of physical properties in the circumferential direction.

The second base material layer is composed of, for example, a single layer containing polyester having butylene terephthalate as a main repeating unit. According to the tubular method described above, since the unstretched raw fabric is formed into a film at a high cooling rate, a low crystallinity can be maintained even when the unstretched raw fabric is composed of a single layer. Therefore, the unstretched raw fabric can be stably stretched.

By including PBT as a main component in the second base material layer, the heat resistance of the laminate can be increased. For example, the tensile modulus of the laminate can be made sufficiently high. In particular, it is possible to sufficiently increase the tensile modulus of elasticity (hereinafter also referred to as hot tensile modulus) of the laminate in a high-temperature atmosphere, for example, an atmosphere of 100°C.

Advantages of the second base material layer containing PBT as a main component as in the above-described second and third configurations will be described below.

PBT is excellent in heat resistance. For this reason, it is possible to suppress the deformation of the second base material layer and the reduction in the strength of the second base material layer when the packaging bag containing the contents such as food is subjected to boiling treatment or retort treatment. can. The retort treatment is a process in which the packaging bag is heated under pressure after filling the contents into the packaging bag and sealing the packaging bag. The temperature of the retort treatment is, for example, 120° C. or higher. The boiling process is a process in which the contents are filled into a packaging bag, the packaging bag is sealed, and then the packaging bag is boiled in hot water under atmospheric pressure. The boiling treatment temperature is, for example, 60° C. or higher and 100° C. or lower.

Also, the second base material layer has high strength. Therefore, as in the case where the packaging material 8 constituting the packaging bag contains nylon, the packaging bag can be endowed with puncture resistance.

[Sealant layer]
The sealant layer is arranged on the content side of the packaging bag when manufacturing the packaging bag using the laminate, and has a function of sealing the laminates together. The sealant layer comprises fossil fuel derived linear low density polyethylene (LLDPE) and fossil fuel derived low density polyethylene (LDPE). In addition, the sealant layer has excellent impact resistance and excellent Hand cutting property can be compatible.

The sealant layer may further contain biomass-derived linear low-density polyethylene in addition to fossil fuel-derived linear low-density polyethylene and fossil fuel-derived low-density polyethylene. By including the biomass-derived linear low-density polyethylene in the sealant layer, the environmental load can be further reduced.

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 or more and 25% by mass or less, more preferably 10% by mass or more and 20% by mass. % by mass or less. In addition, the content of biomass-derived and/or fossil fuel-derived linear low-density polyethylene in the sealant layer (if two types are included, the total content) is preferably 75% by mass or more and 95% by mass or less, and more Preferably, it is 80% by mass or more and 90% by mass or less. By mixing the low-density polyethylene and the linear low-density polyethylene in the above ratio in the sealant layer, both excellent impact resistance and excellent hand tearability can be achieved when the packaging bag is produced.

The sealant layer preferably has a biomass degree of 5% or more and 30% or less, more preferably 10% or more and 25% or less, still more preferably 15% or more and 20% or less. In the present invention, the term "biomass degree" indicates the weight ratio of biomass-derived components. If the degree of biomass is within the above range, it is possible to reduce the amount of fossil fuel used and reduce the environmental load while keeping costs down.

The above biomass degree is a value indicated by weight ratio, but it is a value of C14 content obtained by a radioactive carbon (C14) measuring method based on ASTM-D6866. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in all carbon atoms in the sealant layer, the ratio of biomass-derived carbon can be calculated. In the present invention, when the content of C14 in the sealant layer is P _C14 , the content P _bio of biomass-derived carbon is expressed by the following formula P _bio (%)=P _C14 /105. 5 x 100
can be obtained by The biomass degree of polyethylene produced using ethylene, which is a biomass-derived raw material, may be expressed as a weight ratio or as a value obtained by measuring the content of biomass-derived carbon by radiocarbon (C14) measurement. same value.

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

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

In the present invention, biomass-derived fermented ethanol refers to purified ethanol produced by contacting a culture medium containing a carbon source obtained from a plant material with a microorganism that produces ethanol or a product derived from a crushed product thereof. Conventionally known methods such as distillation, membrane separation, and extraction can be applied to purify ethanol from the culture medium. For example, a method of adding benzene, cyclohexane or the like to cause azeotropy or removing water by membrane separation or the like can be mentioned.

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

Linear low-density polyethylene and low-density polyethylene are less than 0.93 g/cm ³ , preferably 0.91 g/cm ³ or more and less than 0.93 g/cm ³ , more preferably 0.912 g/cm ³ or more and 0.928 g /cm ³ or less, more preferably 0.915 g/cm ³ or more and 0.925 g/cm ³ or less. Note that the MFR of linear low-density polyethylene may be lower than the MFR of low-density polyethylene. The densities of linear low-density polyethylene and low-density polyethylene are values measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the linear low-density polyethylene and the low-density polyethylene have a density of 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 it can be used as the inner layer of the packaging bag. It can be used preferably. Also, 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 can be increased, and it can be suitably used as the inner layer of the packaging bag.

Linear low-density polyethylene and low-density polyethylene are 0.1 g/10 minutes or more and 10 g/10 minutes or less, preferably 0.2 g/10 minutes or more and 9 g/10 minutes or less, more preferably 1 g/10 minutes or more8. It has a melt flow rate (MFR) of 5 g/10 minutes or less. Note that 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 method A under conditions of a temperature of 190° C. and a load of 21.18 N in the method specified in JIS K7210-1995. If the MFR of the linear low-density polyethylene and the low-density polyethylene is 0.1 g/10 minutes or more, the extrusion load during molding can be reduced. Moreover, if the MFR of linear low-density polyethylene and low-density polyethylene is 10 g/10 minutes or less, the mechanical strength of the sealant layer can be enhanced.

In the present invention, the biomass polyethylene that is preferably used is a biomass-derived linear low-density polyethylene manufactured by Braskem (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%), Braskem biomass-derived linear low-density polyethylene (trade name: SLH218, density: 0.916 g/cm ³ , MFR: 2.3 g/10 min, biomass degree 87%), Braskem biomass-derived Low-density polyethylene (trade name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree 95%), Braskem biomass-derived low-density polyethylene (trade name: SPB681, density : 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%), biomass-derived low-density polyethylene manufactured by Braskem (trade name: STN7006, density: 0.923 g/cm ³ , MFR: 0.6 g/10 minutes, biomass degree 95%), and the like.

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

As the biomass polyethylene, a biomass-derived linear low-density polyethylene manufactured by Braskem (trade name: SLL118, density: 0.916 g/cm ³ , MFR: 1.0 g/10 min, biomass degree 87%), Braskem Biomass-derived linear low-density polyethylene (trade name: SLL318, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min, biomass degree 87%), Braskem biomass-derived linear low-density polyethylene (trade name: SLH218, density: 0.916 g/cm ³ , MFR: 2.3 g/10 min, biomass content: 87%).

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

The sealant layer may be a single layer or multiple layers. When the biomass-derived linear low-density polyethylene as described above is used for the sealant layer, the sealant layer may have three layers, an inner layer, an intermediate layer, and an outer layer. In this case, it is preferable that the intermediate layer is made of biomass-derived linear low-density polyethylene, and the inner and outer layers are made of conventionally known fossil fuel-derived linear low-density polyethylene.

The thickness of the sealant layer is preferably 40 μm or more and 80 μm or less, more preferably 45 μm or more and 70 μm or less. If the thickness of the sealant layer is within the above range, sufficient sealability can be imparted when the packaging bag is produced.

[Barrier layer]
Next, the barrier layer will be explained. As the barrier layer constituting the laminate of the present invention, a metal foil or an inorganic or inorganic oxide deposited layer can be suitably used.

(metal foil)
A conventionally known metal foil can be used as the metal foil constituting the barrier layer. Aluminum foil is preferable from the viewpoint of gas barrier properties that prevent permeation of oxygen gas and water vapor, and light shielding properties that prevent permeation of visible light, ultraviolet rays, and the like. Moreover, since it is possible to impart a metallic luster to the packaging bag, it is possible to improve the design. The thickness of the metal foil is, for example, 5 μm or more and 15 μm or less.

(evaporation layer)
The inorganic or inorganic oxide deposited layer is a layer composed of a deposited film that can be formed by a conventionally known method. By providing the vapor deposition layer, it is possible to impart or improve gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like. Note that the barrier layer may include two or more vapor deposition layers. When two or more deposited layers are provided, they may have the same composition or may have different compositions.

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

Although the film thickness of the metal vapor deposition film varies depending on the type of metal used, it is desirable to select and form it within the range of, for example, 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. More specifically, in the case of a deposited aluminum film, the film thickness is desirably 50 Å or more and 600 Å or less, more preferably 100 Å or more and 450 Å or less.

Examples of transparent deposition films include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), titanium ( Ti), lead (Pb), zirconium (Zr), yttrium (Y), and other oxide films can be used. In particular, for packaging bags, it is preferable to have a deposited film of aluminum oxide or silicon oxide.

Inorganic oxides are represented by MO _X such as SiO _X and AlO _X (wherein M represents an inorganic element, and the value of X varies depending on the inorganic element). expressed. The range of values of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), Potassium (K) is 0 to 0.5, Tin (Sn) is 0 to 2, Sodium (Na) is 0 to 0.5, Boron (B) is 0 to 1.5, Titanium (Ti) can range from 0 to 2, lead (Pb) from 0 to 2, zirconium (Zr) from 0 to 2, and yttrium (Y) from 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and not transparent, and the upper limit of the range of X is the fully oxidized value. Silicon (Si) and aluminum (Al) are preferably used for packaging materials, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. values can be used.

The film thickness of the transparent deposited film varies depending on the type of inorganic oxide used, etc., but it is desirable to select and form it within the range of, for example, 50 Å or more and 2000 Å or less, preferably 100 Å or more and 1000 Å or less. For example, in the case of a deposited film of aluminum oxide or silicon oxide, the film thickness is desirably 50 Å or more and 500 Å or less, more preferably 100 Å or more and 300 Å or less.

The vapor deposition film can be formed on the substrate layer or the like using the following forming method. Examples of methods for forming a deposited film include physical vapor deposition methods such as vacuum deposition, sputtering, and ion plating (physical vapor deposition, PVD), plasma chemical vapor deposition, thermochemical vapor deposition, and the like. A chemical vapor deposition method (Chemical Vapor Deposition method, CVD method) such as a chemical vapor deposition method and a photochemical vapor deposition method can be used.

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

As the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , at least one of partial hydrolyzate of alkoxide and condensate of hydrolysis of alkoxide can be used. The partial hydrolyzate of the above alkoxide does not need to have all of the alkoxy groups hydrolyzed, and may be those in which one or more alkoxy groups are hydrolyzed, or a mixture thereof. As the condensate obtained by hydrolysis of alkoxide, a partially hydrolyzed alkoxide dimer or higher, specifically a dimer to hexamer, is used.

In the alkoxide represented by the general formula R ¹ _n M(OR ² ) _m , the metal atom represented by M can be silicon, zirconium, titanium, aluminum, or the like. In this embodiment, preferred metals include, for example, silicon and titanium. In the present invention, alkoxides can be used either singly or as a mixture of alkoxides of two or more different metal atoms in the same solution.

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

For example, a silane coupling agent may be added when preparing the gas barrier composition. Known organic reactive group-containing organoalkoxysilanes can be used as the silane coupling agent. In this embodiment, organoalkoxysilanes having an epoxy group are particularly preferably used. Specifically, examples include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β -(3,4-Epoxycyclohexyl)ethyltrimethoxysilane and the like can be used. The above silane coupling agents may be used singly or in combination of two or more.

[Print layer]
The printed layer is a layer formed by printing for decoration, display of contents, display of expiration date, display of manufacturer, seller, etc., and for imparting aesthetics. The print layer includes, for example, any desired pattern layer such as pictures, photographs, letters, numerals, graphics, symbols, and patterns. 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 print layer can be provided as necessary, for example, it can be provided between the first substrate layer and the barrier layer. The printed layer may be provided on the entire surface of the first base material layer, or may be provided on a part thereof. The print layer can be formed using conventionally known pigments and dyes, and the formation method is not particularly limited.

The print layer may contain a coloring agent and a cured product of a polyol and an isocyanate compound. In this case, the printed layer may or may not contain a biomass-derived component. When a printed layer containing a cured product of a polyol and an isocyanate compound is formed from a material containing a biomass-derived component, at least one of the polyol as the main agent and the isocyanate compound as the curing agent in the printed layer contains the biomass-derived component. It can be formed using a cured product. In addition, when the printed layer is formed from a material that does not contain a biomass-derived component, the printed layer can be formed using a conventionally known polyol composed of a fossil fuel-derived component and an isocyanate compound composed of a fossil fuel-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 the biomass-derived component. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As polyfunctional alcohols derived from biomass, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugarcane, cassava, and sago palm can be used. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant materials by the following methods. There are 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-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances 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 polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

Biomass-derived polyfunctional carboxylic acids include reproducible plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and the recycling of waste edible oils, etc. Aliphatic polyfunctional carboxylic acids obtained from plant sources such as oils can be used. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced with heptyl alcohol as a by-product by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. In the present embodiment, 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.

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, and ester compounds thereof; In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, and their ester compounds and the like 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 the polyfunctional alcohol and the polyfunctional isocyanate contains the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described in the 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. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also 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 methyl-esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 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 methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate methods. More specifically, the phosgenation method includes a method in which 1,5-pentamethylenediamine or a salt thereof is reacted directly with phosgene, and a hydrochloride of pentamethylenediamine suspended in an inert solvent and reacted with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamate conversion method, first, 1,5-pentamethylenediamine or a salt thereof is carbamate to form pentamethylenedicarbamate (PDC), which is then thermally decomposed to produce 1,5-pentamethylenediisocyanate. Synthesis. In the present embodiment, the polyisocyanate preferably used includes 1,5-pentamethylene diisocyanate-based polyisocyanate (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, 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-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. These may be used alone or in combination of two or more.

[Coloring agent]
The coloring agent is not particularly limited, and conventionally known pigments and dyes can be used.

When the printed layer contains a biomass-derived component, the printed layer preferably has a biomass degree based on a weight ratio of 5% or more, more preferably 5% or more and 50% or less, and even more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

The weight of the printed layer after drying is preferably 0.1 g/m ² or more and 10 g/m ² or less, more preferably 1 g/m ² or more and 5 g/m ² or less, still more preferably 1 g/m ² or more and 3 g/m ² or more. It is below.

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

[Adhesive layer]
The adhesive layer is a layer provided when any two layers are adhered by a dry lamination method. For example, between the first substrate layer and the barrier layer, between the barrier layer and the second substrate layer, and between the second substrate layer and the sealant layer. The adhesive layer can be formed by applying an adhesive to the surface of the layer to be laminated when laminating any two layers and drying the adhesive. Examples of adhesives include one-component or two-component curing or non-curing vinyl, (meth)acrylic, polyamide, polyester, polyether, polyurethane, epoxy, rubber, and others. A solvent-type, water-based, or emulsion-type adhesive can be used. A cured product of a polyol and an isocyanate compound can be used as the two-liquid curing adhesive. In this case, at least either the polyol or the isocyanate compound may contain a biomass-derived component.

As the isocyanate compound containing a biomass-derived component in the adhesive layer, the same isocyanate compound containing a biomass-derived component as in the print layer can be used. Moreover, in the adhesive layer, as the polyol containing the biomass-derived component, the same polyol as that for the above-described print layer can be used. Further, when the laminate has a plurality of adhesive layers, only one layer may be formed from a cured product containing a biomass-derived component, or all adhesive layers may be formed from a cured product containing a biomass-derived component. . The cured product in each adhesive layer may have the same composition or different compositions. Further, 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. Composition is also acceptable.

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

Examples of coating methods for the lamination adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fontaine method, a transfer roll coating method, and other methods. .

The weight of the adhesive layer after drying is preferably 0.1 g/m ² or more and 10 g/m ² or less, more preferably 1 g/m ² or more and 6 g/m ² or less, still more preferably 2 g/m ² or more and 5 g/m 2 or more. ² or less.

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

The adhesive layer may be an adhesive resin layer used when bonding two layers by a sand lamination method. Thermoplastic resins that can be used for the adhesive resin layer include polyethylene-based resins, polypropylene-based resins, cyclic polyolefin-based resins, or copolymer resins, modified resins, or mixtures (including alloys) containing these resins as main components. ) can be used. Polyolefin resins include, for example, low density polyethylene (LDPE), medium density polyethylene (MDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), polypropylene (PP), metallocene catalyst Ethylene-α-olefin copolymer, ethylene-polypropylene random or block copolymer, ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-α-olefin copolymer polymerized using Ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-maleic acid copolymer, ionomer resin, adhesion between layers In order to improve the above, it is possible to use an acid-modified polyolefin resin obtained by modifying the above polyolefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, or itaconic acid. can. 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 singly or in combination of two or more. Cyclic polyolefins such as ethylene-propylene copolymers, polymethylpentene, polybutene, and polynorbonene can be used as cyclic polyolefin resins. These resins can be used singly or in combination. As the polyethylene-based resin described above, the biomass content can be further improved by using the above-described biomass-derived ethylene as a monomer unit.

When the adhesive resin layer is laminated by the melt extrusion lamination 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. The anchor coating agent includes any resin having a heat resistance temperature of 135° C. or higher, such as an anchor coating agent made of vinyl-modified resin, epoxy resin, urethane resin, polyester resin, polyethyleneimine, etc. Especially, An anchor coating agent which 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. In addition, a silane coupling agent may be used together as an additive, and nitrocellulose may be used together to improve heat resistance.

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

[Other layers]
The laminate may further include a thermoplastic resin layer or the like as another layer. As the thermoplastic resin layer, polyethylene resin, polypropylene resin, or cyclic polyolefin resin, or copolymer resin, modified resin, or mixture (including alloy) containing these resins as main components may be used. can be done.

<Method for manufacturing laminate>
The method for producing the laminate according to the present invention is not particularly limited, and it can be produced using a conventionally known method such as a dry lamination method or a sand lamination method.

The laminate according to the present invention is imparted with chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubricating functions, optical functions, thermal functions, surface functions such as biocompatibility, and the like. For the purpose, it is also possible to apply secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metallizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Also, the laminate according to the present invention can be subjected to lamination (dry lamination or extrusion lamination), bag making, and other post-treatments to produce a molded product.

<Packaging bag>
A packaging bag according to the present invention includes the laminate described above. For example, using the above laminate, folding it in two, or preparing two laminates, overlapping the sealant surfaces with each other, and further sealing the peripheral edge thereof, for example, a side seal type , 2-side seal type, 3-side seal type, 4-side seal type, envelope seal type, palm seal type (pillow seal type), pleated seal type, flat bottom seal type, square bottom seal type, gusset type, etc. By heat-sealing with, various forms of packaging bags can be produced.

In the above, the heat sealing can be carried out by known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing.

In the above, the heat sealing can be carried out by known methods such as bar sealing, rotary roll sealing, belt sealing, impulse sealing, high frequency sealing and ultrasonic sealing.

Since the packaging bag has excellent impact resistance and hand tearability while exhibiting a high degree of biomass, it can be suitably used as a packaging bag, particularly a refillable pouch.

A packaging bag according to the present invention will be described with reference to the drawings. An example of a schematic front view of a pouch according to the present invention is shown in FIG.
The refill pouch 100 shown in FIG. 4 is made in the form of a standing pouch. (which may be the same as or different from the film) 103 is folded inward and inserted up to the bottom film folded portion 102 to form a gusset portion 104, and near the lower ends of both sides of the bottom film folded inward. In this case, semi-circular bottom film cutouts 103a and 103b are provided, and the gusset 104 is heat-sealed with a ship bottom-shaped bottom sealing portion 105 whose inside is curved linearly concave from both sides to the center. to form. The body of the pouch is formed by heat-sealing the edges on both sides of the front and rear wall films 101 and 101' with the side seal portions 106a and 106b, and one corner portion of the upper portion of the pouch 100 (Fig. 4), the outer periphery is heat-sealed with the spout sealing portion 107, and has a tapered shape and a narrow spout portion 110 facing obliquely outward and upward. 109b is provided to protrude. The upper portion of the pouch 100 where the spout portion 110 is not provided is heat-sealed with the upper seal portion 108. Since this portion is used as a filling port for the content, it is not filled before the content is filled. It is used as an opening for sealing, and is heat-sealed after filling with contents. In the above example, the refill pouch 100 is configured using two wall films and one bottom film, but one film or two films are used to configure the refill pouch. You may make it

The refill pouch 100 has a half-cut line 111 and a notch 112 at the upper end of the half-cut line 111 as an easy-to-open means at the unsealing position on the tip side of the spout part 110 . In addition, the half-cut line 111 is one or two, and a plurality of half-cut lines, such as one to three on each side of the central half-cut line, are arranged in parallel or converge to the central half-cut line. It can be provided in any shape, such as a shape in which a plurality of parallel half-cut lines and diagonal half-cut lines crossing the half-cut lines are combined.

In order to pour out the contents from the refill pouch, the pouring port 110 is opened to form a pouring port. may be attached by means such as heat sealing. As shown in FIG. 5, the pouring assisting member 200 is made of a gutter-shaped elastic member having an opening 201 in the longitudinal direction. A protruding piece 203 having at least a flat lower surface is provided in the longitudinal direction, and a bottom portion 202 is formed thin as shown. As shown in FIG. 5, the surface of the bottom portion 202 facing the opening 201 and the surface of each projecting piece 203 facing the opening 201 are attached to the wall film 101'. In consideration of the mounting strength, at least the surfaces of the protruding pieces 203 facing the opening 201 should be mounted on the wall film 101'.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the description of the Examples below as long as it does not exceed the gist thereof.

[Example 1]
As the first base material layer, a biaxially stretched PET film (biomass degree based on radiocarbon (C14) measurement: 13 %, thickness 12 μm) was prepared. Subsequently, a printed layer was formed by gravure printing on the surface of the PET film that would be located on the inner surface side when constructing the packaging bag. A biaxially stretched nylon film (thickness: 15 μm) was prepared as the second base material layer. In addition, an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., thickness 7 μm) was prepared as a barrier layer.

In addition, as the sealant layer, 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 20 parts by mass of low-density polyethylene (density: 0.924 g/cm ³ , MFR: 2.0 g/10 min, biomass degree: 0%) and biomass-derived linear low-density polyethylene (LLDPE, manufactured by Braskem, commercial product) Name: SLL118, density: 0.916 g/cm ³ , MFR: 1.0 g/10 min, biomass content: 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-blown air-cooled inflation co-extrusion film forming machine to obtain a polyethylene film (thickness: 110 μm, biomass content: 17.4%) for a sealant layer.

Subsequently, a PET film, an aluminum foil, a biaxially oriented nylon film, and a polyethylene film were laminated in this order by a dry lamination method to produce a laminate 10 shown in FIG. The layer structure of this laminate 10 is expressed as follows.
Bio PET/Mark/DL/ALM/DL/ONy/DL/Bio PE
"/" represents the boundary between layers. The layer on the left end is a layer forming the outer surface of the laminate, and the layer on the right end is a layer forming the inner surface of the laminate.
"Bio-PET" means PET derived from biomass. "Mark" means printed layer. "DL" means adhesive layer containing adhesive. "ONy" means nylon. "ALM" means aluminum foil. "Bio-PE" means a polyethylene film comprising biomass-derived linear low density polyethylene, fossil fuel-derived linear low density polyethylene, and fossil fuel-derived low density polyethylene.

[Example 2]
A laminate 10 shown in FIG. 1 was produced in the same manner as in Example 1, except that the following polyethylene film (thickness: 60 μm) was used as the sealant layer. As the polyethylene film, one prepared as follows was used. First, 80 parts by mass of linear low-density polyethylene derived from fossil fuel (density: 0.918 g/cm ³ , MFR: 3.8 g/10 min, degree of biomass: 0%) and low-density polyethylene derived from fossil fuel ( Density: 0.924 g/cm ³ , MFR: 2.0 g/10 min, biomass content: 0%) 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-blown air-cooled inflation co-extrusion film-forming machine to obtain a polyethylene film (thickness: 60 μm, biomass content: 0%) for a sealant layer.
The layer structure of the laminate 10 is expressed as follows.
Bio PET/Mark/DL/ALM/DL/ONy/DL/PE
"PE" means polyethylene film comprising linear low density polyethylene derived from fossil fuel and low density polyethylene derived from fossil fuel.

[Comparative Example 1]
As the first base material layer, a biaxially stretched PET film (biomass degree: 0%, Toyobo Co., Ltd., E5102, thickness 12 μm) formed using fossil fuel-derived terephthalic acid and fossil fuel-derived ethylene glycol. A laminate 10 shown in FIG. 1 was produced in the same manner as in Example 1, except that . The layer structure of the laminate 10 is expressed as follows.
Fossil PET/Mark/DL/ONy/DL/ALM/DL/Bio PE
"Fossil PET" means PET derived from fossil fuels.

<Manufacturing of pouches>
The laminate obtained in Example 1 was used as a wall film and a bottom film, the sealant layers were heat-sealed, and a pouring assisting member as shown in FIG. 5 was attached to the inner surface of the wall film. A standing pouch with a pouring aid member shown in was produced. Similarly, using the laminates obtained in Example 2 and Comparative Example 1, a standing pouch with a pouring aid member shown in FIG. 4 was produced.

<Impact resistance test>
Each pouch obtained above was filled with 200 cc of water and heat-sealed to seal. These pouches were then repeatedly dropped from a height of 1.2 m 10 times with the bottom facing down and evaluated according to the following criteria. The evaluation results are shown in Table 1.
(Evaluation criteria)
◯: The pouch was not broken.
x: The pouch was broken.

<Hand tearability test>
Using the laminates obtained in Examples 1 and 2 and Comparative Example 1, three standing pouches with a pouring aid shown in FIG. 4 were prepared in the same manner as described above. Next, using the notch provided at the spout portion of the standing pouch as a base point, the hand tearability when cutting along the half-cut line was confirmed.
(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.

Table 1 shows the results of the above performance evaluation test.

10, 20 laminate 11, 21 first substrate layer 12, 22 barrier layer 13, 23 second substrate layer 14, 24 sealant layer 25 print layer 26, 27 adhesive layer 100 refill pouch 101, 101' wall film 102 Bottom film folded part 103 Bottom film 103a, 103b Bottom film notch part 104 Gusset part 105 Bottom seal part 106a, 106b Side seal part 107 Spout part seal part 108 Top seal part 109a, 109b Notch part 110 Spout part 111 Half-cut line 112 Notch 200 Extraction assisting member 201 Opening 202 Bottom portion 203 Protruding piece

Claims (7)

A laminate comprising at least a first substrate layer, a barrier layer, a second substrate layer, and a sealant layer in this order,
The first base material layer contains polyethylene terephthalate having biomass-derived ethylene glycol as a diol unit and fossil fuel-derived terephthalic acid as a dicarboxylic acid unit,
The sealant layer includes a fossil fuel-derived linear low-density polyethylene and a fossil fuel-derived low-density polyethylene,
the barrier layer comprises a metal foil;
The laminate, wherein the second base material layer has a thickness of 9 μm or more and 15 μm or less . 2. The laminate of Claim 1, wherein the second substrate layer comprises polyamide or polybutylene terephthalate. The laminate according to claim 1 or 2, wherein the sealant layer includes biomass-derived linear low-density polyethylene, fossil fuel-derived linear low-density polyethylene, and fossil fuel-derived low-density polyethylene. The laminate according to any one of claims 1 to 3, wherein the sealant layer contains 5% by mass or more and 25% by mass or less of low-density polyethylene derived from fossil fuel. The laminate according to claim 3 or 4, wherein the sealant layer contains a total of 75% by mass or more and 95% by mass or less of linear low-density polyethylene derived from biomass and linear low-density polyethylene derived from fossil fuel. 6. The laminate according to any one of claims 1 to 5, further comprising a print layer between the first substrate layer and the barrier layer. A packaging bag comprising the laminate according to any one of claims 1 to 6.

Images