JP7240646B2 - Laminate provided with polyolefin resin layer and packaging product provided with the same - Google Patents

Description

The present invention relates to a laminate provided with a polyolefin resin layer containing biomass polyolefin, and more particularly, at least a substrate layer, an anchor coat layer, and biomass-derived ethylene directly laminated on the anchor coat layer. and a polyolefin resin layer containing a biomass polyolefin that is a polymer of the monomer containing the polyolefin resin layer. Furthermore, it relates to packaging products and flexible packaging comprising the laminate.

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. Biomass is an organic compound that is photosynthesised from carbon dioxide and water, and is a so-called carbon-neutral renewable energy that is regenerated into carbon dioxide and water by using it. In recent years, biomass plastics using biomass as raw materials have been rapidly put to practical use, and attempts have been made to produce various resins from biomass raw materials.

As a biomass-derived resin, polylactic acid (PLA), which is produced through lactic acid fermentation, began commercial production first, but its performance as a plastic, including its biodegradability, has fallen behind that of today's general-purpose plastics. Since it is very different from the standard, it has not been widely used due to limitations in product applications and product manufacturing methods. In addition, PLA is subjected to Life Cycle Assessment (LCA) evaluation, and discussions are being made on energy consumption during PLA production and equivalence when replacing general-purpose plastics.

Here, various kinds of general-purpose plastics such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene are used. In particular, polyethylene is molded into films, sheets, bottles, etc., and is used in various applications such as packaging materials, and is widely used around the world. Therefore, the use of conventional fossil fuel-derived polyethylene imposes a large environmental load.

Therefore, it is desired to reduce the consumption of fossil fuels by using biomass-derived raw materials for the production of polyethylene. For example, until now, research has been conducted to produce ethylene and butylene, which are raw materials for polyolefin resins, from renewable natural raw materials (see, for example, Patent Document 1).

Japanese Patent Publication No. 2011-506628

The present inventors focused on ethylene, which is the raw material of polyolefin resin, and instead of ethylene obtained from conventional fossil fuels, biomass polyolefin (hereinafter simply referred to as "biomass polyolefin") using biomass-derived ethylene as the raw material A laminate comprising a polyolefin resin layer containing a polyolefin resin layer made of polyolefin produced using ethylene obtained from conventional fossil fuel (hereinafter sometimes simply referred to as "fossil fuel-derived polyolefin") Polyolefin resin layer It was found that a laminate having physical properties such as mechanical properties comparable to a laminate having The present invention is based on such findings.

Accordingly, an object of the present invention is to provide a laminate comprising a polyolefin resin layer containing biomass polyolefin, which is comparable in physical properties such as mechanical properties to conventional laminates comprising a polyolefin resin layer made of polyolefin derived from fossil fuel. That is.

In aspects of the invention,
A laminate comprising at least a substrate layer, an anchor coat layer, and a polyolefin resin layer directly laminated on the anchor coat layer in this order,
The polyolefin resin layer is composed only of biomass-derived low-density polyethylene, or composed of a mixed resin of biomass-derived low-density polyethylene and fossil fuel-derived low-density polyethylene,
A laminate having a biomass degree of 5% or more in the polyolefin resin layer (provided that it is composed of a biomass polyester resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the diol unit is biomass-derived ethylene glycol).

In an embodiment of the present invention, the polyolefin resin layer contains 5% by mass or more and 100% by mass or less of the biomass-derived low-density polyethylene and 0% by mass or more and 95% by mass or less of the fossil fuel-derived low-density polyethylene. is preferred.

In the aspect of this invention, it is preferable that the thickness of the said anchor coat layer is 0.5 micrometer or less.

In the aspect of the present invention, the material of the anchor coat layer is preferably a material selected from the group consisting of organic titanium, polyurethane, polyethyleneimine, polybutadiene, and modified polyolefin.

In the aspect of this invention, it is preferable that the said base material layer contains the resin material selected from the group which consists of polyester, polyolefin, and polyamide.

In another aspect of the present invention, the method for manufacturing the laminate,
A method for producing a laminate is provided, comprising forming an anchor coat layer on the base material layer and then melt extruding a polyolefin resin layer on the anchor coat layer.

In another aspect of the invention, a packaged product is provided comprising the laminate.

Another aspect of the present invention provides flexible packaging comprising the laminate.

The laminate according to the present invention includes at least a base material layer, an anchor coat layer, and a polyolefin resin layer containing biomass polyolefin directly laminated on the anchor coat layer. The amount can be reduced, and the environmental load can be reduced. In addition, since the laminate according to the present invention is comparable in physical properties such as mechanical properties to conventional laminates of polyolefin resin derived from fossil fuel, it can be used as a substitute for laminates of conventional polyolefin resin derived from fossil fuel. be able to.

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. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention; FIG. 1 is a simplified diagram showing an example of the configuration of a standing pouch; FIG. It is a simplified diagram showing an example of the configuration of a laminate tube.

In the present invention, “biomass polyolefin” and “polyolefin resin layer containing biomass polyolefin” refer to those using biomass-derived raw materials as raw materials at least in part, and all of the raw materials are derived from biomass. does not mean

<Laminate>
A laminate according to the present invention comprises a substrate layer, an anchor coat layer, and a polyolefin resin layer containing biomass polyolefin directly laminated on the anchor coat layer in this order. Since the laminate includes a polyolefin resin layer containing biomass polyolefin, it is possible to reduce the amount of fossil fuel used compared to conventional laminates, thereby reducing the environmental load. In addition, the laminate according to the present invention is comparable in terms of physical properties such as mechanical properties to conventional polyolefin resin laminates produced from raw materials obtained from fossil fuels. can be substituted for

The laminate according to the present invention may further have at least one other layer such as a print layer, a barrier layer, a plastic film, an adhesive layer, a thermoplastic resin layer, etc., in addition to the above layers. When two or more other layers are provided, they may have the same composition or may have 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.
A laminate 10 shown in FIG. 1 includes a substrate layer 11 , an anchor coat layer 12 , and a polyolefin resin layer 13 directly formed on the anchor coat layer 12 . In the case of flexible packaging comprising the laminate 10, the polyolefin resin layer 13 is positioned inside the flexible packaging. Here, the polyolefin resin layer 12 is a polyolefin resin layer containing biomass polyolefin.
A laminate 20 shown in FIG. 2 includes a substrate layer 11, a barrier layer 14, an anchor coat layer 12, and a polyolefin resin layer 13 directly formed on the anchor coat layer 12 in this order. In the case of flexible packaging comprising the laminate 20, the polyolefin resin layer 13 is positioned inside the flexible packaging.
A laminate 30 shown in FIG. 3 includes a substrate layer 11, a plastic film 15, an anchor coat layer 12, and a polyolefin resin layer 13 directly formed on the anchor coat layer 12 in this order. In the case of flexible packaging comprising the laminate 30, the polyolefin resin layer 13 is positioned inside the flexible packaging.
Any laminate may be further laminated with a printed layer or a thermoplastic resin layer. When laminating the printed layer and the thermoplastic resin layer, the thermoplastic resin layer may be laminated so as to be the outermost surface.
Each layer constituting the laminate will be described below.

(Base material layer)
In the present invention, the substrate layer functions as a substrate layer that holds the polyolefin resin layer, and is preferably capable of imparting strength to the laminate as a packaging product. As the substrate layer, a resin substrate, preferably a plastic film made of a resin material such as a polyester such as polyethylene terephthalate, a polyolefin such as polyethylene or polypropylene, or a polyamide such as nylon can be used. You may use it in combination of 2 or more types. Moreover, when combining 2 or more types, you may laminate|stack using the dry lamination method, and you may laminate|stack using the melt extrusion method. The thickness of the base layer can be 5 μm or more and 38 μm or less, preferably 5 μm or more and 25 μm or less, more preferably 8 μm or more and 16 μm or less.

The substrate layer may contain a biomass-derived material, or may contain a fossil fuel-derived material.

The base material layer may contain a biomass polyester having a biomass-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. The base material layer may further contain a fossil fuel-derived polyester having a fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

The “biomass degree” (biomass-derived carbon concentration) in 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 the polyester, the ratio of biomass-derived carbon can be calculated. In the present invention, the biomass-derived carbon content Pbio can be determined as follows, where PC14 is the content of C14 in the polyester.
Pbio (%) = PC14/105.5 x 100

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, so only ethylene glycol derived from biomass is used. is used, the biomass-derived carbon content Pbio in the polyester is 20%. In the present invention, the content of biomass-derived carbon measured by radioactive carbon (C14) is preferably 10% or more and 20% or less, more preferably 10% or more and 19% or less, relative to the total carbon in the biomass polyester. There may be. When the content of biomass-derived carbon in the biomass polyester is 10% or more, it is suitable as a carbon offset material. Further, the content of biomass-derived carbon 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 becomes 0%.

The degree of biomass in the substrate layer is 5% or more, preferably 10% or more, and more preferably 15% or more. If the degree of biomass in the substrate layer is 5% or more, the amount of polyester derived from fossil fuels can be reduced compared to conventional methods, and the environmental load can be reduced.

A resin composition of biomass polyester or a resin composition containing biomass polyester and fossil fuel-derived polyester can be used to form a film by, for example, a T-die method to form a substrate layer.

(biomass polyester)
A biomass polyester consists of a diol unit and a dicarboxylic acid unit, and is obtained by a polycondensation reaction using biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid unit.

Biomass-derived ethylene glycol is produced from biomass-derived ethanol (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by a method in which biomass ethanol is converted into ethylene glycol via ethylene oxide by a conventionally known method. Also, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be preferably used.

The dicarboxylic acid unit of biomass polyester uses the dicarboxylic acid derived from a fossil fuel. As dicarboxylic acids, aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and derivatives thereof can be used without limitation. Examples of aromatic dicarboxylic acids include terephthalic acid and isophthalic acid. Examples of derivatives of aromatic dicarboxylic acids include lower alkyl esters of aromatic dicarboxylic acids, specifically methyl esters, ethyl esters, propyl esters and butyl esters. Ester etc. are mentioned. Among these, terephthalic acid is preferred, and dimethyl terephthalate is preferred as the aromatic dicarboxylic acid derivative.

(Polyolefin resin layer)
In the present invention, the polyolefin resin layer contains a biomass polyolefin that is a polymer of a monomer containing biomass-derived ethylene, and may further contain a fossil fuel-derived polyolefin. The polyolefin resin layer may contain 5 mass% or more and 100 mass% or less of biomass polyolefin and 0 mass% or more and 95 mass% or less of fossil fuel-derived polyolefin with respect to the entire polyolefin resin layer, and 5 mass% or more and 100 mass% or less. It may contain less than 0% by mass of biomass polyolefin and more than 0% by mass and 95% by mass or less of fossil fuel-derived polyolefin, and 25% by mass or more and 75% by mass or less of biomass polyolefin and 25% by mass or more and 75% by mass or less of fossil fuel. It may also contain a polyolefin derived from. It suffices if the polyolefin resin layer as a whole can achieve the following biomass degree. In the present invention, since the polyolefin resin layer contains biomass polyolefin, it is possible to reduce the amount of polyolefin derived from fossil fuels and reduce the environmental load compared to the prior art.

In the present invention, the “biomass degree” (biomass-derived carbon concentration in biomass polyolefin) in the polyolefin resin 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 all carbon atoms in the polyolefin, the ratio of biomass-derived carbon can be calculated. In the present invention, the biomass-derived carbon content _Pbio can be determined as follows, where _Pc14 is the content of C14 in the polyolefin.
P _bio (%) = P _C14 /105.5 x 100

In the present invention, theoretically, if all biomass-derived ethylene is used as the raw material for polyolefin, the biomass degree is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. In addition, the biomass-derived carbon concentration in the fossil-fuel-derived polyolefin produced only from fossil-fuel-derived raw materials is 0%, and the biomass degree of the fossil-fuel-derived polyolefin is 0%.

In the present invention, the degree of biomass in the polyolefin resin layer is 5% or more, preferably 10% or more, more preferably 15% or more, and still more preferably 20% or more. In addition, the biomass degree in a polyolefin resin layer does not need to be 100%. This is because if biomass-derived raw materials are used for at least a part of the laminate, the purpose of the present invention is to reduce the amount of fossil fuel used compared to the conventional method. If the degree of biomass in the polyolefin resin layer is 5% or more, it is possible to reduce the amount of polyolefin derived from fossil fuels and reduce the environmental load compared to conventional methods.

The polyolefin resin layer preferably has a weight of 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, more preferably 0.911 g/cm ³ or more and 0.928 g/cm ³ or less, and still more preferably 0.915 g/cm ³ or more. It has a density of 0.925 g/cm ³ or less. The density of the polyolefin resin layer is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the density of the polyolefin resin layer is 0.91 g/cm ³ or more and 0.93 g/cm ³ or less, processing and molding can be facilitated.

The polyolefin resin layer has a thickness of 5 μm or more and 100 μm or less, preferably 10 μm or more and 60 μm or less, more preferably 15 μm or more and 40 μm or less. If the thickness of the polyolefin resin layer is within the above range, the function of adhering the two layers can be sufficiently achieved.

(biomass polyolefin)
In the present invention, the biomass polyolefin is a polymer of monomers containing biomass-derived ethylene. As the biomass-derived ethylene, it is preferable to use one obtained by the production method described below. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyolefin is derived from biomass. Note that the polyolefin raw material monomer does not have to contain 100% by mass of biomass-derived ethylene.

The monomer that is the raw material for the biomass polyolefin may further contain a fossil fuel-derived ethylene monomer and/or a fossil fuel-derived α-olefin monomer, or may further contain a biomass-derived α-olefin monomer.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, and preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyolefin has alkyl groups as a branched structure, so that it can be made more flexible than a simple straight-chain polyolefin.

As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more of them may be mixed and used. In particular, the biomass polyolefin is preferably polyethylene. This is because the use of ethylene, which is a biomass-derived raw material, theoretically enables production from 100% biomass-derived components.

The biomass polyolefin may contain two or more biomass polyolefins with different biomass degrees, and the biomass degree of the entire polyolefin resin layer may be within the above range.

The biomass polyolefin is preferably 0.91 g/cm ³ or more and 0.93 g/cm 3 or less, more preferably 0.912 g/cm ^{3 or} more and 0.928 g/cm ³ or less, still more preferably 0.915 g/cm 3 or more and 0.928 g/cm ³ or more. It has a density of 0.925 g/cm ³ or less.
The density of biomass polyolefin is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the biomass polyolefin has a density of 0.91 g/cm ³ or more, the rigidity of the polyolefin resin layer containing the biomass polyolefin can be increased, and it can be suitably used as an inner layer of packaging products. Also, if the density of the biomass polyolefin is 0.93 g/cm ³ or less, the transparency and mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be enhanced, and it can be suitably used as the inner layer of packaging products.

The biomass polyolefin has a melt flow of 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 more and 8.5 g/10 minutes or less. rate (MFR). 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 biomass polyolefin is 0.1 g/10 minutes or more, the extrusion load during molding can be reduced. Moreover, if the MFR of the biomass polyolefin is 10 g/10 minutes or less, the mechanical strength of the polyolefin resin layer containing the biomass polyolefin can be increased.

In the present invention, the biomass polyolefin that is preferably used is a biomass-derived low-density polyethylene manufactured by Braskem (trade name: SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree 95%), Braskem's biomass-derived low-density polyethylene (trade name: SPB681, density: 0.922 g/cm ³ , MFR: 3.8 g/10 min, biomass degree 95%), and the like.

(Method for producing ethylene derived from biomass)
In the present invention, the method for producing biomass-derived ethylene, which is a raw material for biomass polyolefin, is not particularly limited, and can be obtained by a conventionally known method. An example of a method for producing biomass-derived ethylene will be described below.

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.

In order to obtain the ethylene of the present invention, at this stage, further purification such as reducing the total amount of impurities in ethanol to 1 ppm or less may be performed.

A catalyst is usually used to obtain ethylene by the dehydration reaction of ethanol, but the catalyst is not particularly limited, and conventionally known catalysts can be used. Advantageous in terms of process is a fixed bed flow reaction in which the catalyst and product can be easily separated, and for example, γ-alumina is preferred.

Since this dehydration reaction is an endothermic reaction, it is usually carried out under heating conditions. Although the heating temperature is not limited as long as the reaction proceeds at a commercially useful reaction rate, a temperature of preferably 100° C. or higher, more preferably 250° C. or higher, and even more preferably 300° C. or higher is suitable. Although the upper limit is not particularly limited, it is preferably 500° C. or lower, more preferably 400° C. or lower from the viewpoint of energy balance and equipment.

The reaction pressure is also not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction is suitable for easy separation of the catalyst, but a liquid phase suspension bed, a fluidized bed, or the like may also be used.

In the dehydration reaction of ethanol, the yield of the reaction depends on the amount of water contained in ethanol supplied as a raw material. In general, when a dehydration reaction is performed, it is preferable that there is no water in consideration of water removal efficiency. However, it has been found that in the case of ethanol dehydration using a solid catalyst, the amount of other olefins, especially butene, tends to increase in the absence of water. It is presumed that this is probably because ethylene dimerization after dehydration cannot be suppressed unless a small amount of water exists. The lower limit of the allowable water content should be 0.1% or more, preferably 0.5% or more. Although the upper limit is not particularly limited, it is preferably 50% by mass or less, more preferably 30% or less, and still more preferably 20% or less from the viewpoint of material balance and heat balance.

By carrying out the dehydration reaction of ethanol in this way, a mixed portion of ethylene, water and a small amount of unreacted ethanol is obtained. Ethylene can be obtained by removing water and ethanol. This method may be performed by a known method.

Ethylene obtained by gas-liquid separation is further distilled, and the distillation method, operating temperature, residence time, etc. are not particularly limited except that the operating pressure at this time is normal pressure or higher.

When the raw material is biomass-derived ethanol, the resulting ethylene contains carbonyl compounds such as ketones, aldehydes, and esters, which are impurities mixed in the ethanol fermentation process, and carbon dioxide, which is a decomposition product thereof. Nitrogen-containing compounds such as amines and amino acids, which are contaminants, and ammonia, which are decomposition products thereof, are contained in extremely small amounts. Depending on the use of ethylene, these trace amounts of impurities may pose a problem, so they may be removed by refining. The purification method is not particularly limited, and a conventionally known method can be used. A suitable purification operation is, for example, an adsorption purification method. The adsorbent to be used is not particularly limited, and conventionally known adsorbents can be used. For example, a material with a high surface area is preferable, and the type of adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of biomass-derived ethanol.

As a method for purifying impurities in ethylene, caustic water treatment may be used in combination. If caustic water is to be treated, it is desirable to do so before adsorption purification. In that case, after the caustic treatment, it is necessary to apply moisture removal treatment before adsorption purification.

(Method for producing biomass polyolefin)
In the present invention, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and conventionally known methods can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, vary depending on the type of polyethylene desired, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ), and linear low-density polyethylene (LLDPE) can be appropriately selected depending on the difference in density and branching.
For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

The above-mentioned single-site catalyst is a catalyst capable of forming uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a non-metallocene-based transition metal compound with an activating cocatalyst. . A single-site catalyst has a more uniform active site structure than a multi-site catalyst, and is therefore preferable because it can polymerize a polymer having a high molecular weight and a highly uniform structure. As the single-site catalyst, it is particularly preferable to use a metallocene-based catalyst. The metallocene catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, an organometallic compound if necessary, and each catalyst component of a carrier. be.

In the transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. . Substituted cyclopentadienyl groups include hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl-substituted alkyl groups, silyl-substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups and halosilyl groups. It has at least one substituent selected from groups and the like. The substituted cyclopentadienyl group may have two or more substituents, and the substituents are bonded to each other to form a ring such as an indenyl ring, a fluorenyl ring, an azulenyl ring, hydrogenated forms thereof, and the like. may be formed. A ring formed by combining substituents with each other may further have a substituent with each other.

In the transition metal compound of group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, hafnium and the like, with zirconium and hafnium being particularly preferred. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other by a bridging group. The bridging group includes an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, a substituted silylene group such as a diarylsilylene group, and a substituted germylene group such as a dialkylgermylene group and a diarylgermylene group. A substituted silylene group is preferred.

In the transition metal compounds of Group IV of the periodic table, typical examples of ligands other than ligands having a cyclopentadienyl skeleton include hydrogen, hydrocarbon groups having 1 to 20 carbon atoms (alkyl groups , an alkenyl group, an aryl group, an alkylaryl group, an aralkyl group, a polyenyl group, etc.), a halogen, a metaalkyl group, a metaaryl group, and the like.

One or a mixture of two or more of the transition metal compounds of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton can be used as a catalyst component.

The co-catalyst is one that can make the above Group IV transition metal compound of the periodic table effective as a polymerization catalyst, or one that can balance the ionic charges in a catalytically activated state. Examples of co-catalysts include benzene-soluble aluminoxanes of organoaluminumoxy compounds, benzene-insoluble organoaluminumoxy compounds, ion-exchange layered silicates, boron compounds, cations containing or not containing active hydrogen groups, and non-coordinating anions. ionic compounds, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing a fluoro group.

The transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton may be supported on an inorganic or organic compound carrier and used. As the carrier, porous oxides of inorganic or organic compounds are preferred, and specific examples include ion-exchange layered silicates such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ and B ₂ O. ₃ , CaO, ZnO, BaO, _ThO2 , etc. or mixtures thereof.

Examples of organometallic compounds that may be used if necessary include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organic aluminum is preferably used.

Various additives other than the main component polyolefin may be added to the biomass polyolefin as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, 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 with respect to the entire biomass polyolefin.

(Anchor coat layer)
The anchor coat layer can be formed by applying an anchor coating agent on the surface of the base material layer and drying it when the polyolefin resin layer is laminated on the base material layer by a melt extrusion lamination method or the like. 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 a vinyl-modified resin, an epoxy resin, a urethane resin, a polyester resin, or the like. A two-liquid curing anchor coating agent (polyurethane type) comprising a polyacrylic or polymethacrylic resin having a hydroxyl group 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 thickness of the anchor coat layer is 0.5 μm or less (dry state), preferably 0.1 μm or less (dry state).

(Thermoplastic resin layer)
The thermoplastic resin layer can be formed using a conventionally known thermoplastic resin. By further comprising a thermoplastic resin layer, the laminate has heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties similar to those of conventional laminates. be able to.

Examples of thermoplastic resins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. Copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ionomer resin, polyester resin, polyvinyl chloride resin, polystyrene resin, nylon, etc. Low density polyethylene, linear low density polyethylene, medium density polyethylene, and ethylene-methacrylic acid copolymer are preferred.

The thermoplastic resin layer may contain a biomass-derived material or a fossil fuel-derived material. When the thermoplastic resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of a biomass-derived ethylene-containing monomer, similarly to the polyolefin resin layer.

Further, as described above, a thermoplastic resin layer may be provided on the surface of the substrate layer opposite to the polyolefin resin layer.

(Print layer)
The printed layer contains letters, numbers, patterns, figures, symbols, patterns, etc. It is a layer that forms any desired printed pattern. The printed layer can be provided as necessary, for example, it can be provided on the base material layer. The printed layer may be provided on the entire surface of the 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.

(barrier layer)
The barrier layer is composed of an inorganic substance and/or an inorganic oxide, preferably a deposited film of an inorganic substance or an inorganic oxide, or a metal foil. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and the composition and formation method are not particularly limited. By further including a barrier layer in the laminate, it is possible to impart or improve a gas barrier property that prevents permeation of oxygen gas and water vapor, and a light shielding property that prevents permeation of visible light, ultraviolet light, and the like. Note that the laminate may have two or more barrier layers. When there are two or more barrier layers, they may have the same composition or different compositions.

Examples of deposited 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), or the like, or a deposited film of an inorganic oxide. In particular, as materials suitable for packaging materials (bags) and the like, vapor-deposited films of aluminum metal, or vapor-deposited films of silicon oxide, aluminum metal, or aluminum oxide are preferably used.

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 1, 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.

In the present invention, the film thickness of the vapor-deposited film of the inorganic substance or inorganic oxide as described above varies depending on the type of the inorganic substance or inorganic oxide used. It is desirable to select and form arbitrarily within the range of. More specifically, in the case of a vapor deposited film of aluminum, 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. 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.

A vapor deposition film can be formed on a plastic film such as polyethylene terephthalate or nylon 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.

Also, according to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. A conventionally known metal foil can be used as the metal foil. 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.

(plastic film)
In the present invention, various plastic films may be used as other layers. For example, an oriented polyethylene terephthalate film, an oriented nylon film, an oriented polypropylene film, a nylon 6/meta-xylylenediamine nylon 6 coextruded and coextended film, or a polypropylene/ethylene-vinyl alcohol copolymer coextruded and coextended film, or the like, or A composite film obtained by laminating two or more of these films may be used. The plastic film may be coated with polyvinyl alcohol or the like.

The plastic film may contain materials derived from biomass or may contain materials derived from fossil fuels. When the plastic film contains a biomass-derived material, it may further contain a fossil fuel-derived polyester having a fossil fuel-derived ethylene glycol as a diol unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

(adhesive layer)
The adhesive layer can be an adhesive layer formed by applying an adhesive to the surface of the layer to be laminated and drying it when two layers are adhered by a dry lamination method.
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. Examples of coating methods for the lamination adhesive include direct gravure roll coating, gravure roll coating, kiss coating, reverse roll coating, fonten method, transfer roll coating, and other methods to form a laminate. It can be applied to the coated side of the layer. The coating amount is preferably 0.1 g/m ² or more and 10 g/m ² or less (dry state), more preferably 1 g/m ² or more and 5 g/m ² or less (dry state).

The adhesive layer may be an adhesive resin layer used for bonding two layers by a sand lamination method or a melt extrusion 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. Needless to say, as the above-described polyethylene-based resin, one using the above-described biomass-derived ethylene as a monomer unit can be used.

The adhesive resin layer may contain a biomass-derived material or a fossil fuel-derived material. When the adhesive resin layer contains a biomass-derived material, it may contain biomass polyolefin, which is a polymer of a biomass-derived ethylene-containing monomer, similarly to the polyolefin resin layer.

(Laminate manufacturing method)
The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by using conventionally known methods such as dry lamination, melt extrusion lamination, and sand lamination. In the present invention, it is preferable to laminate other layers via a melt-extruded polyolefin resin layer using a sand lamination method. Alternatively, the polyolefin resin layer and another layer may be laminated by a co-extrusion method.

The thickness of the laminate obtained as described above is arbitrary according to its use, but is usually 5 μm or more and 500 μm or less, preferably 20 μm or more and 300 μm or less.

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.

(Application)
The laminate according to the present invention can be used for packaging products, and is preferably used for flexible packaging such as packaging bags, laminated tubes, lids, and the like. As packaging bags, for example, standing pouch type, side seal type, two side seal type, three side seal type, four side seal type, envelope pasted seal type, palm pasted seal type (pillow seal type), plaited seal type, flat bottom seal. Packaging bags of various forms such as type, square bottom seal type, gusset type and the like are exemplified. The thickness of the laminate in that case can be appropriately determined according to the application, and for example, it is used in the form of a film having a thickness of 30 μm or more and 300 μm or less, preferably 35 μm or more and 180 μm or less.

(Flexible packaging)
The laminate according to the present invention can be suitably used for flexible packaging, particularly packaging bags and laminated tubes. A case where a packaging bag, such as a standing pouch as an example, is formed using the laminate according to the present invention will be described. FIG. 4 is a simplified diagram showing an example of the configuration of a standing pouch.
As shown in FIG. 4 , the standing pouch 40 is composed of two body portions (side sheets) 41 and a bottom portion (bottom sheet) 42 . In the standing pouch 40, the side sheet 41 and the bottom sheet 42 may be composed of the same member, or may be composed of different members. Side sheet 41 and bottom sheet 42 of standing pouch 40 can be formed using a laminate according to the present invention.

Next, the case of forming a laminate tube using the laminate according to the present invention will be described. FIG. 5 is a simplified diagram showing an example of a laminate tube. As shown in FIG. 5 , the laminate tube 50 has a head portion 51 and a cylindrical body portion 32 . The head portion 51 is composed of a hollow conical shoulder portion 53 and a spout portion 54, which are integrally formed. The cylindrical body portion 52 is connected to the shoulder portion 53 of the head portion 51 . The cylindrical body portion 52 can be formed using a laminate in which at least a thermoplastic resin layer, a base material layer, and a polyolefin resin layer are laminated in order.

(Other aspects)
In another aspect of the invention,
A laminate comprising at least a substrate layer, an anchor coat layer, and a polyolefin resin layer directly laminated on the anchor coat layer in this order,
The polyolefin resin layer contains a biomass polyolefin that is a polymer of a monomer containing biomass-derived ethylene,
A laminate is provided in which the polyolefin resin layer has a biomass content of 5% or more.

In another aspect of the present invention, it is preferable that the polyolefin resin layer further contains polyolefin derived from fossil fuel.

In another aspect of the present invention, the polyolefin resin layer preferably contains 5% to 100% by mass of the biomass polyolefin and 0% to 95% by mass of the fossil fuel-derived polyolefin.

In another aspect of the present invention, the polyolefin resin layer preferably contains polyethylene.

In another aspect of the present invention, the anchor coat layer preferably has a thickness of 0.5 μm or less.

In another aspect of the present invention, the material of the anchor coat layer is preferably a material selected from the group consisting of organic titanium, polyurethane, polyethyleneimine, polybutadiene, and modified polyolefin.

In another aspect of the present invention, the substrate layer preferably contains a resin material selected from the group consisting of polyesters, polyolefins, and polyamides.

In another aspect of the present invention, the method for manufacturing the laminate,
A method for producing a laminate is provided, comprising forming an anchor coat layer on the base material layer and then melt extruding a polyolefin resin layer on the anchor coat layer.

In another aspect of the invention, a packaged product is provided comprising the laminate.

Another aspect of the present invention provides flexible packaging comprising the laminate.

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples.

<Measurements/Conditions>
In the following reference examples, reference comparative examples, examples, and comparative examples, the degree of biomass is the value of biomass-derived carbon concentration measured by radioactive carbon (C14).

The conditions of the extrusion film-forming machine used below were as follows.
Screw diameter: 90mm
Screw type: full flight L/D: 28
T-die: 11S type straight manifold T-die effective opening length: 560mm

[Example 1]
<Production of Laminate 1>
A polyethylene terephthalate film derived from fossil fuel (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base material layer, and a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075, polyurethane-based film) was applied to the corona-treated surface. ) to form an anchor coat layer. Subsequently, on the anchor coat layer, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) was applied at 320 ° C. Melt extrusion lamination is performed at a resin temperature and a line speed of 100 m/min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), and a laminate in which a base layer, an anchor coat layer, and a polyolefin resin layer are laminated in order. Got 1 body.

[Example 2]
<Production of laminate 2>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). to form an anchor coat layer. Subsequently, on the anchor coat layer, 50 parts by mass of biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) and A mixed resin obtained by dry blending 50 parts by mass of low-density polyethylene derived from fossil fuel (LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%, manufactured by Nippon Polyethylene Co., Ltd.) Melt extrusion lamination is performed at a resin temperature of 320°C and a line speed of 100 m/min to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), and the base layer, anchor coat layer, and polyolefin resin layer are laminated in order. A laminated body 2 was obtained.

[Comparative Example 1]
<Production of Laminate 3>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). to form an anchor coat layer. Subsequently, on the anchor coat layer, 320% of fossil fuel-derived low-density polyethylene (LC600A manufactured by Nippon Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%) was applied. A resin layer (biomass content: 0%, thickness: 30 μm) is formed by melt extrusion lamination at a resin temperature of ° C and a line speed of 100 m / min, and a base layer, an anchor coat layer, and a resin layer are laminated in order. Got 3 bodies.

[Example 3]
<Production of Laminate 4>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). to form an anchor coat layer. Subsequently, a low-density polyethylene derived from fossil fuel (LC600A, manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass While extruding the adhesive resin layer (biomass degree: 0%, thickness: 15 μm), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness: 7 μm) was bonded. Subsequently, the aluminum foil was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coating layer. Subsequently, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, degree of biomass: 95%) was applied to the anchor coat layer at 320°C. Melt extrusion lamination is performed at a temperature and a line speed of 100 m/min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), a base material layer, an anchor coat layer, an adhesive resin layer, a barrier layer, and an anchor coat layer. , to obtain a laminate 4 in which the polyolefin resin layers were laminated in order.

[Example 4]
<Production of laminate 5>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). to form an anchor coat layer. Subsequently, a low-density polyethylene derived from fossil fuel (LC600A, manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass While extruding the adhesive resin layer (biomass degree: 0%, thickness: 15 μm), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness: 7 μm) was bonded. Subsequently, the aluminum foil was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coating layer. Subsequently, on the anchor coat layer, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) 50 parts by mass and fossil 320 parts of a mixed resin obtained by dry blending 50 parts by mass of fuel-derived low-density polyethylene (LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%, manufactured by Japan Polyethylene Co., Ltd.) A resin temperature of ° C., a line speed of 100 m / min, melt extrusion lamination to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), a base material layer, an anchor coat layer, an adhesive resin layer, a barrier layer, A laminate 5 was obtained in which an anchor coat layer and a polyolefin resin layer were laminated in this order.

[Comparative Example 2]
<Production of laminate 6>
A fossil fuel-derived polyethylene terephthalate film (manufactured by Toyobo Co., Ltd.: E5100, thickness 12 μm) was prepared as a base layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). to form an anchor coat layer. Subsequently, a low-density polyethylene derived from fossil fuel (LC600A, manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass While extruding the adhesive resin layer (biomass degree: 0%, thickness: 15 μm), an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 1N30, thickness: 7 μm) was bonded. Subsequently, the aluminum foil was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coating layer. Subsequently, a fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Co., Ltd., LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree: 0%) was applied on the anchor coat layer at 320 ° C. melt extrusion lamination at a resin temperature of 100 m / min and a line speed of 100 m / min to form a resin layer (biomass degree: 0%, thickness 30 μm), base material layer, anchor coat layer, adhesive resin layer, barrier layer, anchor coat A laminate 6 was obtained in which a layer and a resin layer were laminated in this order.

[Example 5]
<Production of Laminate 7>
As the aluminum-deposited polyethylene terephthalate film 1, a fossil fuel-derived polyethylene terephthalate film (manufactured by Toray Advanced Film Co., Ltd., 1310, thickness 12 μm) on which an aluminum deposition film was formed was prepared.

A biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). , to form an anchor coat layer. Subsequently, on the anchor coat layer, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%), the aluminum-deposited surface of the aluminum-deposited polyethylene terephthalate film 1 was bonded via this adhesive resin layer (biomass degree: 95%, thickness 15 μm). Subsequently, the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, on the anchor coat layer, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) was applied to a resin at 320 ° C. A polyolefin resin layer (biomass content: 95%, thickness: 30 μm) is formed by melt extrusion lamination at a temperature and a line speed of 100 m/min. A laminate 7 was obtained in which the coat layer and the polyolefin resin layer were laminated in this order.

[Example 6]
<Production of laminate 8>
A biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). , to form an anchor coat layer. Subsequently, on the anchor coat layer, a biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) 50 parts by mass and 50 parts by mass of low-density polyethylene derived from fossil fuel (LC600A, manufactured by Nippon Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%) While extruding a mixed resin obtained by dry-blending the above, the aluminum-deposited surface of the aluminum-deposited polyethylene terephthalate film 1 was bonded via this adhesive resin layer (biomass content: 48%, thickness: 15 μm). Subsequently, the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, on the anchor coat layer, 50 parts by mass of biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 minutes, biomass degree: 95%) and fossil 320 parts of a mixed resin obtained by dry blending 50 parts by mass of fuel-derived low-density polyethylene (LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%, manufactured by Japan Polyethylene Co., Ltd.) A polyolefin resin layer (biomass degree: 48%, thickness 30 μm) is formed by melt extrusion lamination at a resin temperature of ° C. and a line speed of 100 m / min. A laminate 8 was obtained in which the film, the anchor coat layer, and the polyolefin resin layer were laminated in this order.

[Comparative Example 3]
<Production of laminate 9>
A biaxially oriented polypropylene film (manufactured by Toyobo Co., Ltd.: P2161, thickness 20 μm) was prepared as a substrate layer, and the corona-treated surface was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075). , to form an anchor coat layer. Subsequently, a low-density polyethylene derived from fossil fuel (LC600A, manufactured by Japan Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass The aluminum vapor-deposited surface of the aluminum vapor-deposited polyethylene terephthalate film 1 was bonded via this adhesive resin layer (biomass degree: 0%, thickness: 15 μm) while extruding the film (biomass degree: 0%). Subsequently, the polyethylene terephthalate film surface of the aluminum-deposited polyethylene terephthalate film 1 was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coat layer. After that, on the anchor coat layer, fossil fuel-derived low-density polyethylene (LC600A, manufactured by Nippon Polyethylene Co., Ltd., density: 0.918 g/cm ³ , MFR: 7.0 g/10 minutes, biomass degree: 0%) was applied at 320 ° C. A resin layer (biomass degree: 0%, thickness 30 μm) is formed by melt extrusion lamination at a resin temperature of 100 m / min and a line speed of 100 m / min. A laminate 9 was obtained in which the anchor coat layer and the resin layer were laminated in this order.

[Example 7]
<Production of laminate 10>
Biaxially stretched polyester film 1 (biomass degree: 20%, manufactured by Toyobo Co., Ltd., DE024, thickness 12 μm ) was prepared. The corona-treated surface of polyester film 1 was coated with a two-liquid curing anchor coating agent (Mitsui Chemicals: A3210/A3075, polyurethane system) to form an anchor coating layer. Subsequently, on the anchor coat layer, biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 minutes, biomass degree: 95%) was applied at 320 ° C. Melt extrusion lamination is performed at a resin temperature and a line speed of 100 m/min to form a polyolefin resin layer (biomass degree: 95%, thickness 30 μm), and a laminate in which a base layer, an anchor coat layer, and a polyolefin resin layer are laminated in order. Got 10 bodies.

[Example 8]
<Production of laminate 11>
A polyester film 1 was prepared as a substrate layer, and the corona-treated surface thereof was coated with a two-liquid curing anchor coating agent (manufactured by Mitsui Chemicals: A3210/A3075) to form an anchor coating layer. Subsequently, on the anchor coat layer, 50 parts by mass of biomass-derived low-density polyethylene (manufactured by Braskem, SBC818, density: 0.918 g/cm ³ , MFR: 8.1 g/10 min, biomass degree: 95%) and A mixed resin obtained by dry blending 50 parts by mass of low-density polyethylene derived from fossil fuel (LC600A, density: 0.918 g/cm ³ , MFR: 7.0 g/10 min, biomass degree: 0%, manufactured by Nippon Polyethylene Co., Ltd.) Melt extrusion lamination is performed at a resin temperature of 320°C and a line speed of 100 m/min to form a polyolefin resin layer (biomass degree: 48%, thickness 30 μm), and the base layer, anchor coat layer, and polyolefin resin layer are laminated in order. A laminated body 11 was obtained.

[Production Examples 1 to 11]
<Production of packaging bag>
A body member laminate (side sheet) and a bottom member laminate (bottom sheet) shown in Table 1 below were combined to form a standing pouch according to the following steps. Specifically, two side sheets are placed on top of each other so that the thermoplastic resin layer is the innermost layer, and the bottom sheet is inserted between the two side sheets. and the bottom sheet were heat-sealed to produce standing pouches 1 to 11 having the configuration shown in FIG.

(liquid leakage test)
The standing pouches 1 to 11 prepared above were filled with the test liquid (ageless seal check (Mitsubishi Gas Chemical Co., Ltd.)) and stored for 1 hour at normal temperature and humidity, and then visually evaluated for liquid leakage according to the following evaluation criteria. bottom. The evaluation results are shown in Table 1.
(Evaluation criteria)
○: There was no liquid leakage from the heat-sealed portion, and the performance as a standing pouch was good.
x: There was liquid leakage from the heat-sealed portion, and the performance as a standing pouch was poor.

Reference Signs List 10, 20, 30 Laminate 11 Base Material Layer 12 Anchor Coat Layer 13 Polyolefin Resin Layer 14 Barrier Layer 15 Plastic Film 40 Standing Pouch 41 Body 42 Bottom 50 Laminate Tube 51 Head 52 Cylindrical Body 53 Shoulder 54 Spout Department

Claims (7)

A laminate comprising at least a substrate layer, an anchor coat layer, and a polyolefin resin layer directly laminated on the anchor coat layer in this order,
The base material layer is a biaxially oriented polyethylene terephthalate film derived from fossil fuel,
The anchor coat layer is any one of vinyl-modified resin, epoxy resin, urethane resin, and polyester resin,
The polyolefin resin layer is composed only of biomass-derived low-density polyethylene, or composed of a mixed resin of biomass-derived low-density polyethylene and fossil fuel-derived low-density polyethylene,
A laminate having a biomass degree of 5% or more in the polyolefin resin layer (provided that it is composed of a biomass polyester resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, and the diol unit is biomass-derived ethylene glycol). 2. The laminate of claim 1, wherein the polyolefin resin layer comprises 5% to 100% by mass of the low density polyethylene derived from biomass and 0% to 95% by mass of the low density polyethylene derived from fossil fuel. body. The laminate according to claim 1 or 2, wherein the anchor coat layer has a thickness of 0.5 µm or less. 4. The material according to any one of claims 1 to 3, wherein the material of the anchor coat layer is a material selected from the group consisting of organic titanium, polyurethane, polyethyleneimine, polybutadiene, and modified polyolefin. laminate. A method for manufacturing a laminate according to any one of claims 1 to 4 ,
A method for producing a laminate, comprising forming an anchor coat layer on the base material layer, and then melt extruding a polyolefin resin layer on the anchor coat layer. A packaging product comprising a laminate according to any one of claims 1-4 . Flexible packaging comprising the laminate according to any one of claims 1-4 .

Images