JP2018051796A - Laminate and packaging product containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate that has a substrate layer, a printed layer, an adhesive layer, and a sealant layer put on one another in this order, the laminate having an improved biomass level.SOLUTION: A laminate has at least a substrate layer, a printed layer, an adhesive layer, and a sealant layer put on one another in this order. The adhesive layer has a cured product of a polyol and an isocyanate compound, with the isocyanate compound having a biomass-derived component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminate in which at least a base material layer, a printing layer, an adhesive layer, and a sealant layer are sequentially laminated, and more specifically, relates to a laminate in which at least the adhesive layer contains a biomass-derived component. Furthermore, it is related with a packaging product provided with this laminated body.

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

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

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

  Polyesters are widely used in various industrial applications because they are excellent in mechanical properties, chemical stability, heat resistance, transparency, and the like and inexpensive. Polyester is obtained by polycondensation of a diol unit and a dicarboxylic acid unit. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. After the polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource, for example, ethylene glycol is produced industrially from ethylene and terephthalic acid is produced industrially from xylene.

  Recently, attempts have been made to produce polyester from biomass raw materials. For example, what used biomass origin as ethylene glycol which is a monomer component has been put into practical use. It has been proposed to apply a polyester resin containing such a biomass-derived raw material to a packaging material (see Patent Document 2).

Special table 2011-506628 gazette JP 2012-96410 A

  Conventionally, in a laminate in which a base material layer, a printing layer, an adhesive layer, and a sealant layer are sequentially laminated, the printing layer and the adhesive layer are formed of a fossil fuel-derived material, and the biomass degree of the entire laminate is determined. It was the cause of the decrease. Therefore, in the laminated body in which the base material layer, the printing layer, the adhesive layer, and the sealant layer are sequentially laminated, it is required to further increase the biomass degree of the entire laminated body.

  In the laminate in which at least the base material layer, the printing layer, the adhesive layer, and the sealant layer are sequentially laminated, the inventors have formed the laminate by forming at least the adhesive layer from a material containing a biomass-derived component. The knowledge that the whole biomass degree can be raised more was acquired. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a laminate in which a base material layer, a printing layer, an adhesive layer, and a sealant layer are sequentially laminated, and the biomass degree is further increased.

In an embodiment of the present invention,
At least a laminate in which a base material layer, a printing layer, an adhesive layer, and a sealant layer are sequentially laminated,
There is provided a laminate in which the adhesive layer contains a cured product of a polyol and an isocyanate compound, and the isocyanate compound contains a biomass-derived component.

  In the aspect of this invention, it is preferable that the said printing layer contains a coloring agent and the hardened | cured material of a polyol and an isocyanate compound, and at least any one of a polyol or an isocyanate compound contains a biomass origin component.

  In the aspect of this invention, it is preferable that the said base material layer contains a polypropylene.

  In the aspect of the present invention, the sealant layer preferably contains polypropylene.

  In the aspect of the present invention, it is preferable that the adhesive layer has a biomass degree of 30% or more and 50% or less.

  In the aspect of this invention, it is preferable that the biomass degree of the said printing layer is 10% or more and 50% or less.

  In the aspect of this invention, it is preferable that the biomass degree of the said laminated body is 1% or more and 60% or less.

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

  The laminate according to the present invention is a laminate in which at least a base material layer, a print layer, an adhesive layer, and a sealant layer are sequentially laminated, and at least the adhesive layer is formed of a material containing a biomass-derived component. Moreover, the biomass degree of the whole laminated body can be raised more.

It is a schematic cross section which shows an example of the laminated body by this invention.

<Laminate>
The laminate according to the present invention is obtained by laminating at least a base material layer, a printing layer, an adhesive layer, and a sealant layer in this order. By forming at least the adhesive layer with a material containing a biomass-derived component in the laminate, the amount of fossil fuel used can be reduced as compared with the conventional case, and the environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a conventional fossil fuel-derived laminate, and therefore replaces a conventional laminate having a polyester resin layer derived from fossil fuel. be able to.

  In the present invention, the biomass degree described below is preferably 1% or more, more preferably 1% or more and 60% or less, and further preferably 5% or more and 60% or less in the entire laminate. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  The laminate preferably has a thickness of 10 μm to 500 μm, more preferably 30 μm to 300 μm, and still more preferably 40 μm to 200 μm.

  The laminate according to the present invention may further include at least one other layer such as a barrier layer and a resin layer in addition to the above layers. When two or more other layers are included, each may have the same composition or a different composition.

The laminate according to the present invention will be described with reference to the drawings. An example of a schematic cross-sectional view of a laminate according to the present invention is shown in FIG.
A laminate 10 shown in FIG. 1 includes a base material layer 11, a printing layer 12, an adhesive layer 13, and a sealant layer 14.
Hereinafter, each layer which comprises a laminated body is demonstrated.

[Base material layer]
The base material layer is a plastic film. A base material layer can be formed using the following biomass polyester, when forming with the material containing a biomass origin component.

(Biomass polyester)
Biomass polyester uses biomass-derived ethylene glycol as a diol unit and fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. In addition to biomass polyester, the base material layer may further include 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 following biomass degree should just be implement | achieved as the whole base material layer. In the present invention, since the base material layer contains biomass polyester, it is possible to reduce the amount of polyester derived from fossil fuel and reduce the environmental load as compared with the conventional case.

  In the present invention, “biomass degree” indicates the weight ratio of biomass-derived components.

  Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymer obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. Is used, the weight ratio of biomass-derived components in the polyester is about 30%, so the degree of biomass is about 30%. The weight ratio of biomass-derived components 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%.

  In the present invention, the degree of biomass in the base material layer is 5% or more, preferably 10% or more and 30% or less, more preferably 15% or more and 25% or less. If the degree of biomass in the base material layer is 5% or more, the amount of polyester derived from fossil fuel can be reduced and the environmental load can be reduced compared to the conventional case.

  Biomass-derived ethylene glycol uses ethanol (biomass ethanol) produced from biomass as a raw material. For example, biomass-derived ethylene glycol can be obtained from biomass ethanol by a conventionally known method, such as a method of producing ethylene glycol via ethylene oxide. Moreover, you may use commercially available biomass ethylene glycol, for example, the biomass ethylene glycol marketed from India Glycol can be used conveniently.

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

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid. And a chain or alicyclic dicarboxylic acid. Examples of the aliphatic dicarboxylic acid derivative include lower alkyl esters such as methyl ester, ethyl ester, propyl ester and butyl ester of aliphatic dicarboxylic acid, and cyclic acid anhydrides of aliphatic dicarboxylic acid such as succinic anhydride. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and succinic acid as the main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, methyl esters of adipic acid and succinic acid, or a mixture thereof are more preferable. These dicarboxylic acids can be used alone or in combination of two or more.

  The biomass polyester may be a copolymer polyester obtained by adding a copolymer component as a third component in addition to the diol component and the dicarboxylic acid component. Specific examples of the copolymer component include a bifunctional oxycarboxylic acid, a trifunctional or higher polyhydric alcohol, a trifunctional or higher polyvalent carboxylic acid and / or an anhydride thereof, and 3 Examples include at least one polyfunctional compound selected from the group consisting of functional or higher oxycarboxylic acids. Among these copolymer components, a bifunctional and / or trifunctional or higher functional oxycarboxylic acid is particularly preferably used because a copolymer polyester having a high degree of polymerization tends to be easily produced. Among them, the use of a tri- or higher functional oxycarboxylic acid is most preferable because a polyester having a high degree of polymerization can be easily produced with a very small amount without using a chain extender described later.

  Biomass polyester can be obtained by a conventionally known method in which the above-described diol unit and dicarboxylic acid unit are polycondensed. Specifically, after performing the esterification reaction and / or transesterification reaction of the dicarboxylic acid component and the diol component, a general method of melt polymerization such as a polycondensation reaction under reduced pressure, or an organic solvent It can be produced by a known solution heating dehydration condensation method using The amount of the diol used when producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Generally, however, esterification and / or transesterification and / or polycondensation reactions are performed. It is preferable to use an excess amount of 0.1 mol% or more and 20 mol% or less because of the distillation in the inside.

  A base material layer can be formed, for example, by forming a film by a T-die method using a biomass polyester resin composition or a resin composition containing biomass polyester and a fossil fuel-derived polyester. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature of the melting point Tm or higher of the resin composition to a temperature of Tm + 70 ° C. to melt the resin composition, for example, A base layer film can be formed by extruding into a sheet form from a die such as a T die and rapidly solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

  The base material layer is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the base layer film extruded onto the cooling drum as described above is subsequently heated by roll heating, infrared heating, or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The longitudinal stretching is usually performed in a temperature range of 50 ° C. or more and 100 ° C. or less. Further, the ratio of the longitudinal stretching is preferably 2.5 times or more and 4.2 times or less, although it depends on the required characteristics of the film application. When the draw ratio is less than 2.5, the thickness unevenness of the film becomes large and it is difficult to obtain a good film.

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

Breaking strength of the film of the substrate layer in the MD direction 5 kg / mm ² or more 40 kg / mm ² or less, at 35 kg / mm ² or less 5 kg / mm ² or more in the TD direction, elongation at break in the MD direction 50% or more and 350% or less, and 50% or more and 300% or less in the TD direction. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1% or more and 5% or less.

  The base material layer preferably has a thickness of 5 μm to 40 μm, more preferably 8 μm to 25 μm, and still more preferably 9 μm to 20 μm. If the thickness of the base material layer is in the above range, the molding process is easy and it can be suitably used as a packaging material.

  When the base layer is formed of a material not containing a biomass-derived component, for example, a polyester film such as a polyethylene terephthalate film or polybutylene terephthalate, a polyolefin film such as a polyethylene film or a polypropylene film, a nylon film or nylon 6 / metaxylylenediamine A polyamide film such as a nylon 6 co-extrusion co-stretched film, a polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretched film, or a plastic film such as a composite film in which two or more of these films are laminated can be used. The plastic film may be coated with polyvinyl alcohol or the like.

  The base material layer may be a single layer film or a co-pressed film of two or more layers. Moreover, the base material layer may be one in a laminated body, and you may make it include two or more. For example, when two base material layers are contained in a laminated body, one base material layer may be called a base material layer and another base material layer may be called a 2nd base material layer.

[Print layer]
The printed layer can be used to display decorations, contents, display of the best-before period, display of manufacturers, sellers, etc., and display of other characters and letters, numbers, pictures, figures, symbols, patterns, etc. It is a layer for forming a desired arbitrary printed pattern. The printed layer contains a colorant and a cured product of a polyol and an isocyanate compound. When the printing layer is formed of a material containing a biomass-derived component, it can be formed using a cured product in which at least one of a polyol and an isocyanate compound contains a biomass-derived component. Moreover, when forming a printing layer with the material which does not contain a biomass origin component, it can form using the hardened | cured material which both a conventionally well-known polyol and an isocyanate compound consist of a fossil fuel origin component.

(Polyol)
In the present invention, the polyol containing a biomass-derived component includes, for example, a biomass-derived polyfunctional alcohol and / or a fossil fuel-derived polyfunctional alcohol, a biomass-derived polyfunctional carboxylic acid and / or a fossil fuel-derived polyfunctional carboxylic acid. The polyester polyol obtained by reacting can be used, and at least one of a polyfunctional alcohol and a polyfunctional carboxylic acid contains a biomass-derived component.

  As the polyfunctional alcohol derived from biomass, an aliphatic polyfunctional alcohol obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. Examples of the biomass-derived aliphatic polyfunctional alcohol include 1,3-propanediol, 1,4-butanediol, ethylene glycol and the like obtained from plant raw materials by the following method, and any of them can be used. . These may be used alone or in combination.

Biomass-derived 1,3-propanediol (HOCH ₂ CH ₂ CH ₂ OH) is produced from glycerol via 3-hydroxypropyl aldehyde (HPA) by a fermentation method in which glucose is obtained by decomposing plant raw materials. Compared with the 1,3-propanediol compound of the EO production method, 1,3-propanediol compound produced by a biomethod such as the above fermentation method yields a useful by-product such as lactic acid in terms of safety. It is also preferable that the manufacturing cost can be kept low.
Biomass-derived 1,4-butanediol can produce biomass 1,4-butanediol by obtaining succinic acid obtained by producing glycol from plant raw materials and fermenting it, and hydrogenating it.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

  As the polyfunctional alcohol derived from fossil fuel, a compound having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, the polyfunctional alcohol derived from fossil fuel is not particularly limited and conventionally known ones can be used. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1, 6-hexanediol, neopentyl glycol, 1,4-butanediol, 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 are recycled from recyclable soybean oil, linseed oil, tung oil, palm oil, palm oil, castor oil and other plant-derived oils, and waste edible oils mainly composed of them. Aliphatic polyfunctional carboxylic acids obtained from plant materials such as oil can be used. Examples of the biomass-derived aliphatic polyfunctional carboxylic acid include sebacic acid, succinic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced as a by-product of heptyl alcohol by alkaline pyrolysis of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid.

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

(Isocyanate compound)
In this invention, the polyisocyanate obtained from a plant raw material can be used for the isocyanate compound containing a biomass origin component. Biomass-derived polyisocyanate is obtained by acid-amidating a divalent carboxylic acid derived from biomass, converting it to a terminal amino group by reduction, and further reacting with phosgene to convert the amino group to an isocyanate group. . Biomass-derived polyisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. Moreover, biomass-derived isocyanate compounds can also be obtained by converting amino groups into isocyanate groups using biomass-derived amino acids as raw materials. For example, lysine diisocyanate (LDI) can be obtained by converting a carboxyl group of lysine into a methyl ester and then converting an amino group into an isocyanate group. 1,5-pentamethylene diisocyanate (PDI) can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

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

(Coloring agent)
The colorant is not particularly limited, and conventionally known pigments and dyes can be used.

  The printed layer preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, and still more preferably 10% or more and 50% or less. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

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

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

[Adhesive layer]
The adhesive layer is a layer that performs a function of adhering any two layers constituting the laminate, for example, a printed layer and a sealant layer. The adhesive layer includes a cured product of a polyol and an isocyanate compound, the isocyanate compound includes a biomass-derived component, and the polyol preferably includes a biomass-derived component.

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

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

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

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

[Sealant layer]
A sealant layer can be formed using the following biomass polyolefin, when forming with the material containing a biomass origin component. Moreover, when forming a sealant layer with the material which does not contain a biomass origin component, it can form using the conventionally well-known thermoplastic resin derived from a fossil fuel. A sealant layer is a layer which becomes an innermost layer in a laminated body.

  Biomass polyolefin is a polymer of monomers containing olefins such as ethylene derived from biomass. Since a biomass-derived olefin is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass. In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of olefin derived from biomass.

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

  In the present invention, biomass-derived fermented ethanol refers to ethanol that has been purified after contacting a microorganism-producing product or a crushed product thereof with a culture solution containing a carbon source obtained from plant raw materials. For the purification of ethanol from the culture solution, conventionally known methods such as distillation, membrane separation, and extraction can be applied. For example, a method of adding benzene, cyclohexane or the like and azeotropically or removing water by membrane separation or the like can be mentioned.

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

  The α-olefin is not particularly limited, but can usually be one having 3 to 20 carbon atoms, and is preferably butylene, hexene or octene. This is because if it is butylene, hexene or octene, it can be produced by polymerization of ethylene which is a biomass-derived raw material. In addition, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, and therefore can be more flexible than a simple linear one.

  As the biomass polyolefin, polyethylene or a copolymer of ethylene and α-olefin may be used alone, or two or more kinds may be mixed and used. In particular, the biomass polyolefin is preferably polyethylene. This is because, by using ethylene, which is a biomass-derived raw material, it is theoretically possible to manufacture with 100% biomass-derived components.

  The biomass polyolefin may contain two or more kinds of biomass polyolefins having different biomass degrees, and the biomass degree should be within the above range as the whole polyolefin resin layer.

Biomass polyolefin, preferably 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.912 g / cm ³ or more 0.928 g / cm ³ or less, more preferably 0.915 g / cm ³ or more 0 It has a density of 925 g / cm ³ or less. The density of biomass polyolefin is a value measured according to the method prescribed | regulated to A method among JISK7112-1980 after performing annealing as described in JISK6760-1995. If the density of the biomass polyolefin is 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 the inner layer of the packaged product. Moreover, if the density of biomass polyolefin is 0.93 g / cm < ³ > or less, the transparency and mechanical strength of the polyolefin resin layer containing biomass polyolefin can be improved, and it can be used suitably as an inner layer of a packaged product.

  Biomass polyolefin has a melt flow of 0.1 g / 10 min to 10 g / 10 min, preferably 0.2 g / 10 min to 9 g / 10 min, more preferably 1 g / 10 min to 8.5 g / 10 min. It has a rate (MFR). The melt flow rate is a value measured by the method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. If the MFR of the biomass polyolefin is 0.1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of biomass polyolefin is 10 g / 10min or less, the mechanical strength of the polyolefin resin layer containing biomass polyolefin can be raised.

In the present invention, as the biomass polyolefin preferably used, biomass-derived low density polyethylene (trade name: SBC818, density: 0.918 g / cm ³ , MFR: 8.1 g / 10 min, biomass degree) manufactured by Braskem 95%), low density polyethylene derived from biomass by Braskem (trade name: SPB681, density: 0.922 g / cm ³ , MFR: 3.8 g / 10 min, biomass degree 95%), derived from biomass by Braskem Linear low density polyethylene (trade name: SLL118, density: 0.916 g / cm ³ , MFR: 1.0 g / 10 min, biomass degree 87%) and the like.

  Examples of the fossil fuel-derived thermoplastic resin include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, Examples thereof include an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, or an ionomer.

  The sealant layer preferably has a biomass degree of 5% or more, more preferably 5% or more and 60% or less, and still more preferably 10% or more and 60% or less. If the degree of biomass is in the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced.

  The sealant layer preferably has a thickness of 10 μm to 300 μm, more preferably 20 μm to 200 μm, and still more preferably 30 μm to 150 μm.

[Barrier layer]
The laminate according to the present invention may further include a barrier layer. The barrier layer is made of an inorganic substance and / or an inorganic oxide, and is preferably made of a vapor deposited film of an inorganic substance or an inorganic oxide or a metal foil. A vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. When the laminate further includes a barrier layer, gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted or improved. Note that the laminate may have two or more barrier layers. When two or more barrier layers are provided, each may have the same composition or a different composition.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum metal or aluminum oxide vapor-deposited film is preferably used as a packaging material (bag) or the like.

Representation of the inorganic oxide, for _example, SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are suitably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Can be used.

  In the present invention, the film thickness of the inorganic or inorganic oxide vapor-deposited film as described above varies depending on the type of inorganic or inorganic oxide used, but is, for example, 50 to 2000 mm, preferably 100 to 1000 mm. It is desirable to select and form arbitrarily within the range. More specifically, in the case of an aluminum deposited film, the film thickness is preferably 50 to 600 mm, more preferably 100 to 450 mm, and in the case of an aluminum oxide or silicon oxide deposited film, The film thickness is from 50 to 500 mm, more preferably from 100 to 300 mm.

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

  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 preferred from the viewpoints of gas barrier properties that prevent transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent transmission of visible light, ultraviolet light, and the like.

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

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

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

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

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

  The laminate according to the present invention may further include a thermoplastic resin layer as another layer. As the thermoplastic resin layer, the same material as the sealant layer can be used.

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

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

<Application>
The laminate according to the present invention can be used for a packaged product, and examples of the packaged product include a packaging bag, a laminate tube, a lid material, a sheet molded product, and a label material.

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

[Example 1]
<Preparation of laminated body 1>
As a base material layer, on a biaxially stretched polypropylene film derived from fossil fuel (biomass degree 0%, thickness 12 μm), a polyester polyol containing a biomass-derived component as a main agent and a polyisocyanate derived from fossil fuel as a curing agent, A printing layer (biomass degree 25%, weight after drying 2 g / m ² ) was formed using biomass-derived ink to which a colorant (titanium oxide) was further added. Subsequently, a biomass-derived adhesive containing a polyester polyol containing a biomass-derived component as a main agent and a polyisocyanate derived from biomass as a curing agent on a printed layer using a dry laminating method (trade name, manufactured by Mitsui Chemicals, Inc.) : Stavio) is applied, and then an unstretched polypropylene film (biomass degree 0%, thickness 50 μm) derived from fossil fuel is passed through this adhesive layer (biomass degree 35%, weight after drying 2 g / m ² ). The laminated body 1 by which the base material layer, the printing layer, the adhesive bond layer, and the sealant layer were laminated | stacked in order was obtained by bonding.

[Example 2]
<Preparation of laminated body 2>
As a base material layer, on a biaxially stretched polypropylene film derived from fossil fuel (biomass degree 0%, thickness 12 μm), a polyester polyol composed of a component derived from fossil fuel as a main ingredient and a polyisocyanate derived from fossil fuel as a curing agent are included. A printing layer (biomass degree 0%, weight after drying 2 g / m ² ) was formed using an ink derived from fossil fuel further added with a colorant (titanium oxide). Subsequently, a biomass-derived adhesive comprising a biomass-derived polyester polyol as a main agent and a polyisocyanate containing a biomass-derived component as a curing agent on a printed layer using a dry laminating method (trade name, manufactured by Mitsui Chemicals, Inc.) : Stavio) is applied, and then an unstretched polypropylene film (biomass degree 0%, thickness 50 μm) derived from fossil fuel is passed through this adhesive layer (biomass degree 35%, weight after drying 2 g / m ² ). The laminated body 2 by which the base material layer, the printing layer, the adhesive bond layer, and the sealant layer were laminated | stacked in order was obtained by bonding.

[Example 3]
<Preparation of laminate 3>
As a base material layer, on a biaxially stretched polypropylene film derived from fossil fuel (biomass degree 0%, thickness 12 μm), a polyester polyol containing a biomass-derived component as a main agent and a polyisocyanate derived from fossil fuel as a curing agent, A printing layer (biomass degree 25%, weight after drying 2 g / m ² ) was formed using biomass-derived ink to which a colorant (titanium oxide) was further added. Subsequently, after applying a fossil fuel-derived adhesive containing a polyester polyol composed of a fossil fuel-derived component as a main agent and a polyisocyanate derived from a fossil fuel as a curing agent on a printed layer using a dry laminating method, A non-stretched polypropylene film (biomass degree 0%, thickness 50 μm) derived from fossil fuel is bonded through an adhesive layer (biomass degree 0%, dried weight 2 g / m ² ), and a base material layer and printing A laminate 3 was obtained in which a layer, an adhesive layer, and a sealant layer were sequentially laminated.

[Comparative Example 1]
<Preparation of laminate 4>
As a base material layer, on a biaxially stretched polypropylene film derived from fossil fuel (biomass degree 0%, thickness 12 μm), a polyester polyol composed of a component derived from fossil fuel as a main ingredient and a polyisocyanate derived from fossil fuel as a curing agent are included. A printing layer (biomass degree 0%, weight after drying 2 g / m ² ) was formed using an ink derived from fossil fuel further added with a colorant (titanium oxide). Subsequently, after applying a fossil fuel-derived adhesive containing a polyester polyol composed of a fossil fuel-derived component as a main agent and a polyisocyanate derived from a fossil fuel as a curing agent on a printed layer using a dry laminating method, A non-stretched polypropylene film (biomass degree 0%, thickness 50 μm) derived from fossil fuel is bonded through an adhesive layer (biomass degree 0%, dried weight 2 g / m ² ), and a base material layer and printing A laminate 4 was obtained in which a layer, an adhesive layer, and a sealant layer were sequentially laminated.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Base material layer 12 Print layer 13 Adhesive layer 14 Sealant layer

Claims (8)

At least a laminate in which a base material layer, a printing layer, an adhesive layer, and a sealant layer are sequentially laminated,
The laminated body in which an adhesive bond layer contains the hardened | cured material of a polyol and an isocyanate compound, and an isocyanate compound contains a biomass origin component.   The laminate according to claim 1, wherein the print layer includes a colorant and a cured product of a polyol and an isocyanate compound, and at least one of the polyol or the isocyanate compound includes a biomass-derived component.   The laminate according to claim 1 or 2, wherein the base material layer includes polypropylene.   The laminated body as described in any one of Claims 1-3 in which the said sealant layer contains a polypropylene.   The laminated body as described in any one of Claims 1-4 whose biomass degree of the said adhesive bond layer is 30% or more and 50% or less.   The laminated body as described in any one of Claims 1-4 whose biomass degree of the said printing layer is 10% or more and 50% or less.   The laminated body as described in any one of Claims 1-6 whose biomass degree of the said laminated body whole is 1% or more and 60% or less.   Packaged product provided with the laminated body as described in any one of Claims 1-7.

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