JP6721028B2 - Laminate with resin layer derived from biomass - Google Patents

Description

The present invention relates to a laminate provided with a biomass-derived resin layer, and more specifically, a polyester-derived resin layer, an adhesive resin layer, a barrier layer, and a biomass-derived monomer obtained by polymerizing a monomer containing biomass-derived ethylene. The present invention relates to a laminate having a biomass polyolefin resin layer containing polyethylene in this order.

In recent years, with the increasing demand for building a recycling-based society, there is a demand in the materials field to escape from fossil fuels as well as energy, and the use of biomass is drawing attention. Biomass is an organic compound photosynthesized from carbon dioxide and water, and by utilizing it, it becomes carbon dioxide and water again, so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics using these biomasses as raw materials has progressed rapidly, 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, preceded commercial production, but its performance as a plastic, including its biodegradability, is the current general-purpose plastic. Therefore, it is not widely used because there are limits to product applications and product manufacturing methods. Further, life cycle assessment (LCA) evaluation is performed on PLA, and energy consumption during PLA production and equivalence during replacement of general-purpose plastics are discussed.

Here, as the general-purpose plastic, various types such as polyethylene, polypropylene, polyvinyl chloride, and polystyrene are used. In particular, polyethylene is formed into films, sheets, bottles, etc., and is used for various applications such as packaging materials, and is used in large amounts all over the world. Therefore, the use of conventional fossil fuel-derived polyethylene has a large environmental load.

Therefore, it is desired to reduce the amount of fossil fuel used by using a raw material derived from biomass for the production of polyethylene. For example, up to now, research has been conducted on producing ethylene or butylene, which is a raw material of a polyolefin resin, from a renewable natural raw material (for example, see Patent Document 1).

Japanese Patent Publication No. 2011-506628

The present inventors have focused on ethylene, which is a raw material of a polyolefin laminate, and instead of ethylene obtained from a conventional fossil fuel, a laminate having a biomass polyolefin resin layer of polyolefin whose raw material is ethylene derived from biomass The present inventors have found that a laminate of polyolefin resin produced by using ethylene obtained from a conventional fossil fuel is comparable to the physical properties such as mechanical properties. The present invention is based on this finding.

Therefore, an object of the present invention is a biomass polyester resin layer comprising a biomass polyester resin composition containing a polyester composed of a diol unit and a dicarboxylic acid unit as a main component, wherein the diol unit is a biomass-derived ethylene glycol, or A fossil fuel polyester resin layer, which comprises a fossil fuel polyester resin composition containing as a main component a polyester composed of a fossil fuel-derived diol unit and a fossil fuel-derived dicarboxylic acid unit , an adhesive resin layer, and a barrier layer, A polyester resin layer produced from a raw material obtained from a conventional fossil fuel, which is to provide a laminate having a biomass polyolefin resin layer containing carbon-neutral polyethylene using biomass-derived ethylene in this order. Another object of the present invention is to provide a laminate having a polyolefin resin layer and a biomass resin laminate that is comparable to physical properties such as mechanical properties.

That is, according to one aspect of the present invention,
A biomass polyester resin composition comprising a polyester comprising a diol unit and a dicarboxylic acid unit as a main component, wherein the diol unit is a biomass-derived ethylene glycol, or a fossil fuel-derived diol unit. A fossil fuel polyester resin layer comprising a fossil fuel polyester resin composition containing as a main component a polyester comprising a fossil fuel-derived dicarboxylic acid unit, and
Low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, copolymer resin with ethylene/α-olefin polymerized using metallocene catalyst, ethylene/polypropylene copolymer resin, Ethylene/vinyl acetate copolymer resin, ethylene/acrylic acid copolymer resin, ethylene/ethyl acrylate copolymer resin, ethylene/methacrylic acid copolymer resin, ethylene/methyl methacrylate copolymer resin, ethylene/malein Acid copolymer resin, ionomer resin, polyolefin resin, unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, graft polymerization of ester monomer, or copolymerized resin, maleic anhydride polyolefin resin An adhesive resin layer containing one or more selected from the group consisting of resins graft-modified with
A barrier layer containing an inorganic material,
A biomass polyolefin resin layer made of a biomass polyolefin resin composition containing biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene, and having in this order,
A laminate is provided in which the density of the biomass polyolefin resin layer is 0.90 to 0.925 g/cm ³ .
In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains low density polyethylene derived from biomass and/or linear low density polyethylene derived from biomass.
In the aspect of the present invention, the biomass polyolefin resin layer preferably comprises low density polyethylene and linear low density polyethylene.
In the aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer.
In the aspect of the present invention, the barrier layer is preferably made of a metal foil.
In the aspect of the present invention, the polyester resin layer is preferably the biomass polyester resin layer.
In another aspect of the present invention, a packaged product comprising the laminate is provided.

The laminate according to the present invention comprises a biomass polyester resin composition containing as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, the diol unit being a biomass-derived ethylene glycol, a biomass polyester resin layer, or a fossil. A fossil fuel polyester resin layer, an adhesive resin layer, a barrier layer, and a biomass that are made of a fossil fuel polyester resin composition containing a polyester composed of a diol unit derived from fuel and a dicarboxylic acid unit derived from fossil fuel as a main component. A laminate of carbon-neutral biomass resins can be realized by having a laminate including a biomass polyolefin resin layer containing carbon-neutral polyethylene using ethylene derived from the above in this order. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. In addition, the laminate according to the present invention is comparable to the laminate of the resin produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and thus replaces the laminate of the conventional resin. can do.

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

In the present invention, the "biomass polyester resin composition", the "biomass polyester resin layer", the "biomass polyolefin resin composition", and the "biomass polyolefin resin layer" are raw materials derived from biomass at least in part. However, it does not mean that all of the raw materials are derived from biomass.

Laminated body The laminated body according to the present invention comprises a biomass polyester resin composition containing, as a main component, a polyester composed of a diol unit and a dicarboxylic acid unit, and the diol unit is a biomass-derived ethylene glycol, a biomass polyester resin layer, Alternatively, a fossil fuel biomass polyester resin layer, which comprises a fossil fuel polyester resin composition containing a polyester composed of a diol unit derived from fossil fuel and a dicarboxylic acid unit derived from fossil fuel as a main component, and a biomass polyolefin resin layer are included. It will be done. Since the laminate has the biomass polyolefin resin layer, a laminate of carbon-neutral polyolefin resin can be realized. Therefore, the amount of fossil fuel used can be significantly reduced as compared with the conventional one, and the environmental load can be reduced. Further, the laminate according to the present invention is comparable to the laminate of the polyolefin resin produced from the raw material obtained from the conventional fossil fuel in terms of physical properties such as mechanical properties, and thus the laminate of the conventional polyolefin resin. Can be replaced.

A schematic cross-sectional view of an example of the laminate according to the present invention is shown in FIGS. 1 and 2. The laminated body 10 shown in FIG. 1 includes a biomass polyester resin layer 11 and a biomass polyolefin resin layer 12 formed on the biomass polyester resin layer 11. The laminate 20 shown in FIG. 2 is formed on the biomass polyester resin layer 21, the first biomass polyolefin resin layer 22 formed on the biomass polyester resin layer 21, and the first biomass polyolefin resin layer 22. The second biomass polyolefin resin layer 23 is provided in this order. Hereinafter, each layer constituting the laminated body will be described.

Biomass Polyester Resin Layer In the present invention, the biomass polyester resin layer is composed of the following biomass polyester resin composition containing, as a main component, a polyester composed of a diol unit and a dicarboxylic acid unit.

Biomass Polyester The biomass polyester contained in the biomass polyester resin composition comprises diol units and dicarboxylic acid units, and the diol units are biomass-derived ethylene glycol. The dicarboxylic acid unit may be a dicarboxylic acid derived from fossil fuel. Biomass polyester can be obtained by a polycondensation reaction using such biomass-derived ethylene glycol and fossil fuel-derived dicarboxylic acid.

The biomass-derived ethylene glycol is made from 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 and a method of producing ethylene glycol via ethylene oxide. Further, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol can be suitably used.

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

As the aliphatic dicarboxylic acid, specifically, oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc., usually having 2 to 40 carbon atoms. Chain-like or alicyclic dicarboxylic acids. Further, as the derivative of the aliphatic dicarboxylic acid, a lower alkyl ester such as methyl ester, ethyl ester, propyl ester and butyl ester of the above aliphatic dicarboxylic acid, or a cyclic acid anhydride of the above aliphatic dicarboxylic acid such as succinic anhydride may be used. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid or a mixture thereof is preferable, and one containing succinic acid as a main component is particularly preferable. As the derivative of the aliphatic dicarboxylic acid, the methyl ester of adipic acid and succinic acid, or a mixture thereof is more preferable.

These dicarboxylic acids may be used alone or in admixture of two or more.

The biomass polyester may be a copolymerized biomass polyester obtained by adding a copolymerization component as a third component in addition to the above diol component and dicarboxylic acid component. Specific examples of the copolymerization component include a bifunctional oxycarboxylic acid, a polyfunctional alcohol having a functionality of 3 or more for forming a crosslinked structure, a polycarboxylic acid having a functionality of 3 or more, and/or an anhydride thereof, and 3 At least one polyfunctional compound selected from the group consisting of functionally or higher oxycarboxylic acids can be mentioned. Among these copolymerization components, a bifunctional and/or trifunctional or higher functional oxycarboxylic acid is particularly preferably used since a copolyester biomass polyester having a high degree of polymerization tends to be easily produced. Among them, the use of a trifunctional or higher functional oxycarboxylic acid is most preferable because a biomass polyester having a high degree of polymerization can be easily produced in a very small amount without using a chain extender described below.

Further, the above-mentioned biomass polyester may be a high-molecular-weight biomass polyester obtained by chain extension (coupling) of these copolymerized biomass polyesters. As the chain extender, a chain extender such as a carbonate compound or a diisocyanate compound can be used, but the amount thereof is usually 100 mol% of all the monomer units constituting the biomass polyester, and a carbonate bond and a urethane bond. Is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

Specific examples of the carbonate compound include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, dicyclohexyl. Carbonate etc. are illustrated. In addition, carbonate compounds composed of the same or different hydroxy compounds derived from hydroxy compounds such as phenols and alcohols can be used.

Specific examples of the diisocyanate compound include 2,4-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, and xylylene. Known diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate can be used.

The biomass polyester can be obtained by a conventionally known method of polycondensing the above-mentioned diol unit and dicarboxylic acid unit. Specifically, a general method of melt polymerization in which a polycondensation reaction is performed under reduced pressure after an esterification reaction and/or a transesterification reaction between the above dicarboxylic acid component and a diol component, and an organic solvent Can be produced by a known solution heating dehydration condensation method using.

The amount of the diol used in producing the biomass polyester is substantially equimolar to 100 mol of the dicarboxylic acid or its derivative, but in general, esterification and/or transesterification reaction and/or polycondensation reaction Since there is a middle distillate, it is used in an excess of 0.1 to 20 mol %.

The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The timing for adding the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and may be added at the time of charging the raw materials or at the start of depressurization.

As the polymerization catalyst, a compound containing a Group 1 to Group 14 metal element other than hydrogen and carbon in the periodic table is generally used. Specifically, at least one metal selected from the group consisting of titanium, zirconium, tin, antimony, cerium, germanium, zinc, cobalt, manganese, iron, aluminum, magnesium, calcium, strontium, sodium and potassium. Examples thereof include compounds having an organic group such as a carboxylate, an alkoxy salt, an organic sulfonate, or a β-diketonate salt, and an inorganic compound such as the above-mentioned metal oxide and halide, and a mixture thereof. Among these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferable, and titanium compounds, zirconium compounds and germanium compounds are particularly preferable. Further, the catalyst is preferably a liquid compound at the time of polymerization or a compound soluble in the ester low polymer or the biomass polyester because the polymerization rate becomes high if it is in a molten or dissolved state at the time of polymerization.

As the titanium compound, tetraalkyl titanate is preferable, and specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Benzyl titanate and mixed titanates thereof. Further, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium (diisoproxide)acetylacetonate, titanium bis(ammonium lactate)dihydroxide, titanium bis(ethylacetoacetate)diisopropoxide, titanium (triethanolaminate). ) Isopropoxide, polyhydroxytitanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide or a composite oxide containing titanium and silicon is also preferably used. Among these, tetra-n-propyl titanate, tetraisopropyl titanate and tetra-n-butyl titanate, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium bis(ammonium lactate) dihydroxide, polyhydroxytitanium stearate. , Titanium lactate, butyl titanate dimer, titanium oxide, titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) is preferable, and tetra-n-butyl titanate and polyhydroxytitanium stearate are particularly preferable. , Titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, and titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) are preferable.

Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetate hydroxide, zirconium tris(butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium zirconium oxalate, and polyhydroxyzirconium. Stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Alternatively, zirconium oxide or a composite oxide containing zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris(butoxy) stearate, zirconium tetraacetate, zirconium acetate hydroxide, zirconium ammonium oxalate, zirconium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy. Preferred are zirconium tetraisopropoxide, zirconium tetra-n-butoxide and zirconium tetra-t-butoxide.

Specific examples of the germanium compound include inorganic germanium compounds such as germanium oxide and germanium chloride, and organic germanium compounds such as tetraalkoxygermanium. Germanium oxide, tetraethoxygermanium, tetrabutoxygermanium and the like are preferable, and germanium oxide is particularly preferable, from the viewpoint of price and availability.

When using a metal compound as these polymerization catalysts, the amount of the catalyst used is, as the amount of metal with respect to the biomass polyester produced, a lower limit value of usually 5 ppm or more, preferably 10 ppm or more, and an upper limit value of usually 30,000 ppm or less, preferably 1000 ppm or less. , More preferably 250 ppm or less, particularly preferably 130 ppm or less. If the amount of the catalyst used is too large, not only is it economically disadvantageous, but the thermal stability of the polymer is low, while if it is too small, the polymerization activity is low, and the decomposition of the polymer during polymer production is accompanied by it. Are more likely to be triggered. As for the amount of catalyst used here, the amount of the terminal carboxyl groups of the biomass polyester produced decreases as the amount of use decreases, so a method of reducing the amount of catalyst used is a preferred embodiment.

The reaction temperature of the esterification reaction and/or transesterification reaction of the dicarboxylic acid component and the diol component is usually in the range of 150 to 260° C., and the reaction atmosphere is usually an inert gas atmosphere such as nitrogen or argon. .. The reaction pressure is usually atmospheric pressure to 10 kPa. The reaction time is usually about 1 hour to 10 hours.

In the above manufacturing process, a chain extender (coupling agent) may be added to the reaction system. After the completion of polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the biomass polyester obtained by polycondensation.

The high-molecular-weight biomass polyester using these chain extenders (coupling agents) can be produced using known techniques. After completion of the polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and reacted with the biomass polyester obtained by the polycondensation. Specifically, a biomass obtained by catalytically reacting a diol and a dicarboxylic acid has a terminal group substantially having a hydroxyl group and a mass average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. By reacting the polyester prepolymer with the above chain extender, a biomass polyester resin having a higher molecular weight can be obtained. If the weight average molecular weight of the prepolymer is 20,000 or more, the use of a small amount of coupling agent does not cause gelation during the reaction because it is not affected by the remaining catalyst even under severe conditions such as a molten state. A high-molecular-weight biomass polyester can be produced.

The obtained biomass polyester may be solidified and then solid-phase polymerized, if necessary, in order to further increase the degree of polymerization and to remove oligomers such as cyclic trimers. Specifically, after the biomass polyester is made into chips and dried, the biomass polyester is pre-crystallized by heating at a temperature of 100 to 180° C. for about 1 to 8 hours, and subsequently, at a temperature of 190 to 230° C. It is carried out by heating under an inert gas flow or under reduced pressure for 1 to several tens of hours.

The intrinsic viscosity (measured with an ortho-chlorophenol solution at 35° C.) of the biomass polyester obtained as described above is preferably 0.5 dl/g to 1.5 dl/g, and more preferably 0.6 dl. /G to 1.2 dl/g. If the intrinsic viscosity is less than 0.5 dl/g, the mechanical properties required for the biomass polyester film as a semi-transmissive reflective film substrate, such as tear strength, may be insufficient. On the other hand, if the intrinsic viscosity exceeds 1.5 dl/g, the productivity in the raw material manufacturing process and the film forming process will be impaired.

Various additives may be added to the biomass polyester in the production process or to the produced biomass polyester within a range that does not impair the properties thereof, such as a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, and a gloss An eraser, a deodorant, a flame retardant, a weatherproofing agent, an antistatic agent, a yarn friction reducing agent, a release agent, an antioxidant, an ion exchanger, a coloring pigment and the like can be added. These additives are added in the range of 5 to 50% by mass, preferably 5 to 20% by mass, based on the entire biomass polyester resin composition.

The polyester that may be contained in the biomass polyester resin composition at a ratio of 5 to 45% by mass (hereinafter, also referred to as recycled polyester) is composed of a diol unit and a dicarboxylic acid unit, and a diol derived from fossil fuel or a diol unit. A polyester obtained by recycling a product made of a polyester resin obtained by a polycondensation reaction using a biomass-derived ethylene glycol and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit.

Even if the diol unit and the dicarboxylic acid unit are both raw materials derived from fossil fuel (non-biomass polyester), the resin that is the basis of recycled polyester (that is, polyester resin before recycling) is as described above. It may be biomass polyester.

Examples of fossil fuel-derived diols used for the resin that forms the basis of recycled polyester include aliphatic diols, aromatic diols, and derivatives thereof, and those used as the diol unit of conventional biomass polyester are preferably used. can do. The aliphatic diol is not particularly limited as long as it is an aliphatic or alicyclic compound having two OH groups, but the lower limit value of carbon number is 2 or more and the upper limit value is usually 10 or less, preferably 6 The following aliphatic diols may be mentioned. Specific examples include ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol and 1,4-cyclohexanedimethanol. To be These may be used alone or as a mixture of two or more kinds. Among these, ethylene glycol, 1,4-butanediol, 1,3-propylene glycol and 1,4-cyclohexanedimethanol are preferable, and ethylene glycol is particularly preferable.

In the biomass polyester resin composition containing the biomass polyester obtained as described above, the content of carbon derived from the biomass measured by radiocarbon (C14) is 10 to 19% based on the total carbon in the biomass polyester. Is preferred. Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the amount of C14 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 fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all carbon atoms in the biomass polyester. In the present invention, when the content of C14 in the biomass polyester is P _C14 , the content P _bio of carbon derived from biomass is defined as follows.
P _bio (%)=P _C14 /105.5×100

Taking polyethylene terephthalate as an example, since polyethylene terephthalate is obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, only polyethylene glycol derived from biomass is available. when using the content P _{bio Bio} carbon from biomass in the biomass polyester is 20%. In the present invention, the content of carbon derived from biomass by radiocarbon (C14) measurement is preferably 10 to 19% with respect to the total carbon in the biomass polyester resin composition. When the biomass-derived carbon content in the biomass polyester resin composition is less than 10%, the effect as a carbon offset material becomes poor. On the other hand, as described above, the carbon content derived from the biomass in the biomass polyester resin composition is preferably as close as possible to 20%, but from the viewpoint of problems in the manufacturing process of the film and physical properties, the resin is recycled as described above. Since it is preferable to include polyester and additives, the actual upper limit is 18%.

The biomass polyester resin layer is preferably a biomass polyester resin film made of the above-mentioned biomass polyester resin composition. To process the biomass polyester resin composition into a film, a conventional method of forming a film from a polyester resin can be adopted. Specifically, after drying the biomass polyester resin composition described above, the biomass polyester resin composition is supplied to a melt extruder heated to a temperature (Tm) to Tm+70° C. higher than the melting point of the biomass polyester to obtain the biomass polyester resin composition. Is melted and extruded in a sheet form from a die such as a T die, and the extruded sheet is rapidly cooled and solidified by a rotating cooling drum or the like to form a film. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

The biomass polyester resin film is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded on 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 peripheral speed difference between two or more rolls. The longitudinal stretching is usually performed in the temperature range of 50 to 100°C. The longitudinal stretching ratio is preferably 2.5 times or more and 4.2 times or less, though it depends on the required characteristics of the film application. When the draw ratio is less than 2.5 times, the thickness unevenness of the biomass polyester film becomes large and it is difficult to obtain a good film.

The longitudinally stretched film is subsequently subjected to the treatment steps of transverse stretching, heat setting and heat relaxation in order to obtain a biaxially stretched film. The transverse stretching is usually performed in the temperature range of 50 to 100°C. The transverse stretching ratio is preferably 2.5 times or more and 5.0 times or less, though it depends on the characteristics required for this application. When it is less than 2.5 times, it is difficult to obtain a good film because the thickness unevenness of the film becomes large, and when it exceeds 5.0 times, breakage easily occurs during film formation.

After transverse stretching, heat setting treatment is subsequently carried out, but the preferable temperature range for heat setting is Tg+70 to Tm-10°C of the biomass polyester. The heat setting time is preferably 1 to 60 seconds. Further, for applications requiring a low heat shrinkage rate, heat relaxation treatment may be carried out as necessary.

The thickness of the stretched film of the resin film obtained as described above is arbitrary depending on the application, but is usually about 5 to 500 μm. Breaking strength of such a resin film is 5 to 35 kg / mm ² at 5~40kg / ^mm 2, TD direction MD direction, elongation at break, 50 to 350% in MD direction, the TD direction It is 50 to 300%. Further, the shrinkage rate when left for 30 minutes in a temperature environment of 150° C. is 0.1 to 5%. As described above, the biomass polyester resin film used as the biomass resin layer of the laminate according to the present invention has the same physical properties as those of conventional polyester resin films produced only from fossil fuel-derived materials.

Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer preferably contains the following biomass-derived ethylene in an amount of 5% by mass or more, more preferably 5 to 95% by mass, further preferably 25 to 25% by mass based on the entire biomass polyolefin resin layer. It contains 75% by mass. The biomass polyolefin resin layer may be composed of at least two layers, and has, for example, a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side. Both of the seal layer and the core layer of the laminate may be a biomass polyolefin resin layer, or only one of them may be a biomass polyolefin resin layer.

First biomass polyolefin resin layer In the present invention, the first biomass polyolefin resin layer may function as a core layer of the laminate. Since the laminate has the core layer, it can exhibit excellent flexibility without breaking.

The first biomass polyolefin resin layer preferably contains biomass-derived ethylene in an amount of 5% by mass or more, more preferably 5 to 95% by mass, still more preferably 25 to 75% by mass, relative to the entire first biomass polyolefin resin layer. Most preferably, it contains 40 to 75%. If the concentration of the biomass-derived ethylene in the first biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional one, and a carbon-neutral polyolefin resin laminate is realized. it can.

The first biomass polyolefin resin layer is preferably 0.915 to 0.96 g/cm ³ , more preferably 0.92 to 0.955 g/cm ³ , and still more preferably 0.93 to 0.955 g/cm ³ . It has a density. The density of the first biomass polyolefin resin layer is a value measured according to the method specified in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. If the density of the first biomass polyolefin resin layer is 0.915 g/cm ³ or more, the rigidity of the first biomass polyolefin resin layer can be increased. Further, when the density of the first biomass polyolefin resin layer is 0.96 g/cm ³ or less, the transparency and mechanical strength of the first biomass polyolefin resin layer can be increased.

The first biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g/10 minutes, preferably 3 to 25 g/10 minutes, more preferably 4 to 20 g/10 minutes. The melt flow rate is a value measured by the A method under the conditions of a temperature of 190° C. and a load of 21.18 N according to the method defined in JIS K7210-1995. If the MFR of the first biomass polyolefin resin layer is 1 g/10 minutes or more, the extrusion load during molding can be reduced. If the MFR of the biomass polyolefin resin composition is 30 g/10 minutes or less, the mechanical strength of the first biomass polyolefin resin layer can be increased.

The first biomass polyolefin resin layer has a thickness of 10 to 100 μm, preferably 10 to 50 μm, and more preferably 15 to 30 μm.

Second biomass polyolefin resin layer In the present invention, the second biomass polyolefin resin layer may function as a seal layer of the laminate. Since the laminate has the heat-sealing layer, the laminate can be firmly adhered to the other resin film without using an adhesive or the like.

The second biomass polyolefin resin layer preferably contains 5% by mass or more, more preferably 5 to 95% by mass, and further preferably 25 to 75% by mass of biomass-derived ethylene with respect to the entire second biomass polyolefin resin layer. It consists of When the concentration of the biomass-derived ethylene in the second biomass polyolefin resin layer is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

The second biomass polyolefin resin layer has a density of 0.90 to 0.925 g/cm ³ , preferably 0.905 to 0.925 g/cm ³ . The density of the second biomass polyolefin resin layer is a value measured according to the method defined in the method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. When the density of the second biomass polyolefin resin layer is 0.90 g/cm ³ or more, the rigidity of the second biomass polyolefin resin layer can be increased. Moreover, if the density of the second biomass polyolefin resin layer is 0.925 g/cm ³ or less, the transparency and mechanical strength of the second biomass polyolefin resin layer can be increased.

The second biomass polyolefin resin layer has a melt flow rate (MFR) of 1 to 30 g/10 minutes, preferably 3 to 25 g/10 minutes, more preferably 4 to 20 g/10 minutes. The melt flow rate is a value measured by the A method under the conditions of a temperature of 190° C. and a load of 21.18 N according to the method defined in JIS K7210-1995. When the MFR of the second biomass polyolefin resin layer is 1 g/10 minutes or more, the extrusion load during molding can be reduced. If the MFR of the biomass polyolefin resin composition is 30 g/10 minutes or less, the mechanical strength of the second biomass polyolefin resin layer can be increased.

The second biomass polyolefin resin layer has a thickness of 1 to 50 μm, preferably 1 to 20 μm, more preferably 1 to 10 μm.

In the present invention, the first biomass polyolefin resin layer and the second biomass polyolefin resin layer satisfy the following specific relationships in terms of density, thickness, MFR, and biomass degree (ethylene concentration derived from biomass). It is preferable to have.

In the present invention, it is preferable that the density d ₁ of the first biomass polyolefin resin layer and the density d _{2 of} the second biomass polyolefin resin layer satisfy d ₁ >d ₂ . This is because the first biomass polyolefin resin layer functions as a core layer, so that rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so that flexibility is required.

In the present invention, it is preferable that the thickness t ₁ of the first biomass polyolefin resin layer and the thickness t _{2 of} the second biomass polyolefin resin layer satisfy t ₁ >t ₂ . This is because the first biomass polyolefin resin layer functions as a core layer, and thus the thickness is required, and the second biomass polyolefin resin layer functions as a heat-sealing layer, so that it is not necessary to have the same thickness as the core layer.

In the present invention, MFR ₂ of MFR ₁ of the first biomass polyolefin resin layer second biomass polyolefin resin layer _preferably satisfy the MFR 1> MFR _2. This is because the first biomass polyolefin resin layer functions as a core layer, so that rigidity is required, and the second biomass polyolefin resin layer functions as a heat seal layer, so that flexibility is required.

In the present invention, the biomass-derived ethylene concentration C ₁ of the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C _{2 of} the second biomass polyolefin resin layer preferably satisfy C ₁ >C ₂ . Since the first biomass polyolefin resin layer functions as a core layer and has a large thickness and a large amount of ethylene used, the amount of fossil fuel used can be further reduced by increasing the biomass degree of the first biomass polyolefin resin layer. Is.

Biomass-Derived Ethylene In the present invention, the method for producing biomass-derived ethylene, which is a raw material for the biomass-derived polyolefin, is not particularly limited and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing ethylene derived from biomass will be described.

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. The plant raw material is 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, the biomass-derived fermented ethanol refers to ethanol purified after the ethanol-producing microorganism or its crushed product-derived product is brought into contact with a culture solution containing a carbon source obtained from a plant raw material. 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 to carry out azeotropic distillation, 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, advanced purification such as making the total amount of impurities in ethanol 1 ppm or less may be further performed.

A catalyst is usually used when ethylene is obtained by the dehydration reaction of ethanol, but this catalyst is not particularly limited, and a conventionally known catalyst can be used. What is advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated, and for example, γ-alumina and the like are preferable.

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

The reaction pressure is also not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate the subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which the catalyst can be easily separated is preferable, but a liquid phase suspension bed, a fluidized bed or the like may 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 performing a dehydration reaction, it is preferable that there is no water in view of the removal efficiency of water. However, in the case of ethanol dehydration reaction using a solid catalyst, it was found that the amount of other olefins, especially butene, tends to increase in the absence of water. It is speculated that ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the permissible water content is 0.1% or more, preferably 0.5% or more. The upper limit is not particularly limited, but from the viewpoint of mass balance and heat balance, it is preferably 50% by mass or less, more preferably 30% or less, still more preferably 20% or less.

By carrying out the dehydration reaction of ethanol in this way, a mixed part of ethylene, water and a small amount of unreacted ethanol can be obtained. However, since ethylene is a gas at room temperature below about 5 MPa, gas-liquid separation is performed from these mixed parts. Ethylene can be obtained by removing water and ethanol. This method may be a known method.

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

When the raw material is ethanol derived from biomass, the obtained ethylene includes carbon dioxide gas which is a carbonyl compound such as ketones, aldehydes and esters which are impurities mixed in the ethanol fermentation process and carbon dioxide which is a decomposition product thereof, and a decomposition product of an enzyme. A minute amount of impurities such as nitrogen-containing compounds such as amines and amino acids and decomposition products thereof such as ammonia are contained. These trace amounts of impurities may pose a problem depending on the use of ethylene, and may be removed by purification. The purification method is not particularly limited and can be performed by a conventionally known method. As a suitable purification operation, for example, an adsorption purification method can be mentioned. The adsorbent used is not particularly limited, and a conventionally known adsorbent can be used. For example, a material having a high surface area is preferable, and the type of the adsorbent is selected according to the type and amount of impurities in ethylene obtained by the dehydration reaction of ethanol derived from biomass.

Note that caustic water treatment may be used in combination as a method for purifying impurities in ethylene. When treating with caustic water, it is desirable to perform it before adsorption purification. In that case, it is necessary to perform a water removal treatment after the caustic treatment and before the adsorption purification.

Biomass Polyolefin In the present invention, the biomass-derived polyolefin is obtained by polymerizing a biomass-derived monomer containing ethylene. As the biomass-derived ethylene, it is preferable to use the one obtained by the above production method. Since biomass-derived ethylene is used as the raw material monomer, the polymerized polyolefin is derived from biomass. The raw material monomer of the polyolefin does not have to contain 100% by mass of biomass-derived ethylene.

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

The above-mentioned α-olefin is not particularly limited in carbon number, but normally, one having 3 to 20 carbon atoms can be used, and butylene, hexene, or octene is preferable. This is because if butylene, hexene, or octene can be produced by polymerizing ethylene, which is a raw material derived from biomass. Further, by including such an α-olefin, the polymerized polyolefin has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear one.

The above-mentioned polyolefin is preferably polyethylene. This is because it is theoretically possible to produce 100% biomass-derived components by using ethylene, which is a biomass-derived raw material.

The concentration of ethylene derived from biomass in the above-mentioned polyolefin (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the content of carbon derived from biomass by measuring radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant rate (105.5 pMC), the amount of C14 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 fuel contains almost no C14. Therefore, the proportion of carbon derived from biomass can be calculated by measuring the proportion of C14 contained in all carbon atoms in the polyolefin. In the present invention, when the content of C14 in the polyolefin is P _C14 , the content P _bio of carbon derived from biomass can be obtained as follows.
P _bio (%)=P _C14 /105.5×100

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

In the present invention, the biomass-derived polyolefin or the biomass-derived resin layer need not have a biomass degree of 100%. This is because if the biomass-derived raw material is used even in a part of the laminated body, it is in line with the gist of the present invention that the amount of fossil fuel used is reduced compared to the conventional case.

In the present invention, the method for polymerizing the monomer containing biomass-derived ethylene is not particularly limited, and a conventionally known method can be used. The polymerization temperature and the polymerization pressure may be appropriately adjusted depending on the polymerization method and the polymerization apparatus. The polymerization device is also not particularly limited, and a conventionally known device can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The method for polymerizing a polyolefin, particularly an ethylene polymer or a copolymer of ethylene and an α-olefin, is carried out according to the type of the target polyethylene, for example, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE). ), and linear low-density polyethylene (LLDPE), etc., can be appropriately selected depending on the difference in density and branching. For example, as a polymerization catalyst, using a multi-site catalyst such as Ziegler-Natta catalyst, or a single-site catalyst such as a metallocene catalyst, by any one of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ionic polymerization, It is preferable to carry out in one step or in multiple steps of two or more steps.

The above single-site catalyst is a catalyst that can form a uniform active species, and is usually prepared by contacting a metallocene-based transition metal compound or a nonmetallocene-based transition metal compound with an activating cocatalyst. .. The single-site catalyst is preferable since it has a more active site structure than the multi-site catalyst and can polymerize a polymer having a high molecular weight and a high degree of uniformity. As the single-site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene catalyst is a catalyst including 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. is there.

In the transition metal compound of Group IV of the periodic table containing a ligand having the cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. .. Examples of the substituted cyclopentadienyl group include a hydrocarbon group having 1 to 30 carbon atoms, a silyl group, a silyl-substituted alkyl group, a silyl-substituted aryl group, a cyano group, a cyanoalkyl group, a cyanoaryl group, a halogen group, a haloalkyl group, and a halosilyl group. It has at least one kind of 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, and an indenyl ring, a fluorenyl ring, an azulenyl ring, a hydrogenated product thereof or the like can be formed. It may be formed. The ring formed by bonding the substituents to each other may further have a substituent to 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 and hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton is bound to each other by a bridging group. Examples of the bridging group include a substituted silylene group such as an alkylene group having 1 to 4 carbon atoms, a silylene group, a dialkylsilylene group, and 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 compound of Group IV of the periodic table, as a ligand other than the ligand having a cyclopentadienyl skeleton, hydrogen and a hydrocarbon group having 1 to 20 carbon atoms (alkyl group) are typical. , Alkenyl groups, aryl groups, alkylaryl groups, aralkyl groups, polyenyl groups, etc.), halogens, metaalkyl groups, metaaryl groups and the like.

The transition metal compound of Group IV of the periodic table containing the above-mentioned ligand having a cyclopentadienyl skeleton can use one kind or a mixture of two or more kinds as a catalyst component.

The cocatalyst means a compound which can effectively use the above-mentioned transition metal compound of Group IV of the periodic table as a polymerization catalyst or which can balance the ionic charge in a catalytically activated state. As the co-catalyst, a benzene-soluble aluminoxane of an organoaluminum oxy compound, a benzene-insoluble organoaluminum oxy compound, an ion-exchange layered silicate, a boron compound, a cation with or without an active hydrogen group and a non-coordinating anion are used. And lanthanoid salts such as lanthanum oxide, tin oxide, and a phenoxy compound containing a fluoro group.

The group IV transition metal compound of the periodic table containing a ligand having a cyclopentadienyl skeleton may be used by supporting it on an inorganic or organic compound carrier. As the carrier, an inorganic or organic compound porous oxide is preferable, and specifically, an ion-exchange layered silicate such as montmorillonite, SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , B ₂ O. ₃ , CaO, ZnO, BaO, ThO _{2 and the} like, or a mixture thereof.

Further, examples of the organometallic compound used as necessary include organoaluminum compounds, organomagnesium compounds, organozinc compounds and the like. Of these, organic aluminum is preferably used.

As the polyolefin, a polymer of ethylene or a copolymer of ethylene and α-olefin may be used alone or in combination of two or more.

Biomass Polyolefin Resin Composition In the present invention, the biomass polyolefin resin composition contains the above-mentioned polyolefin as a main component. The biomass polyolefin resin composition preferably contains 5% by mass or more, more preferably 5 to 95% by mass, and still more preferably 25 to 75% by mass of ethylene derived from biomass with respect to the entire biomass polyolefin resin composition. is there. When the concentration of biomass-derived ethylene in the biomass polyolefin resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced as compared with the conventional case, and a carbon-neutral polyolefin laminate can be realized.

The biomass polyolefin resin composition may contain two or more kinds of polyolefins having different degrees of biomass, and the biomass polyolefin resin composition as a whole may have a biomass-derived ethylene concentration within the above range.

The biomass polyolefin resin composition may further include a fossil fuel-derived polyolefin obtained by polymerizing a monomer containing fossil fuel-derived ethylene and fossil fuel-derived ethylene and/or α-olefin. That is, in the present invention, the biomass polyolefin resin composition may be a mixture of a biomass-derived polyolefin and a fossil fuel-derived polyolefin. The mixing method is not particularly limited, and the mixing can be performed by a conventionally known method. For example, it may be dry blending or melt blending.

According to an aspect of the invention, the biomass polyolefin resin composition is preferably 5-90 wt%, more preferably 25-75 wt% biomass-derived polyolefin and preferably 10-95 wt%, more preferably 25. ˜75% by mass of fossil fuel-derived polyolefin. Even when the biomass polyolefin resin composition of such a mixture is used, the concentration of ethylene derived from the biomass may be within the above range in the entire biomass polyolefin resin composition.

In the production process of the above biomass polyolefin resin composition, or in the produced biomass polyolefin resin composition, in addition to the polyolefin as the main component, various additives may be added to the extent that the characteristics are not impaired. Good. Examples of the additives include plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weather resistance agents, antistatic agents, thread friction reducing agents, slip agents, release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, etc. can be added. These additives are preferably added in the range of 1 to 20% by mass, preferably 1 to 10% by mass, based on the entire biomass polyolefin resin composition.

Non-biomass polyolefin resin layer The laminate according to the present invention may further have a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer is a resin layer made of a resin material containing a raw material derived from fossil fuel, and has a biomass degree of 0%. When only one of the core layer and the seal layer of the laminate is a biomass polyolefin resin layer, the other may be a non-biomass polyolefin resin layer. The non-biomass polyolefin resin layer can be formed using conventionally known raw materials, and its composition and forming method are not particularly limited. When the laminate further has the non-biomass polyolefin resin layer, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties can be imparted or improved. The laminate may have two or more non-biomass polyolefin resin layers. When it has two or more non-biomass polyolefin resin layers, they may have the same composition or different compositions.

Examples of the non-biomass polyolefin resin layer 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. Resins such as copolymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers or ionomers can be used. These resins may be formed by an extrusion laminating method, or a film formed in advance by a T-die method or an inflation method may be laminated with a heat resistant substrate layer by a dry laminating method or an extrusion laminating method. ..

Also, stretched polyethylene terephthalate film, silica vapor deposition stretched polyethylene terephthalate film, alumina vapor deposition stretched polyethylene terephthalate film, stretched nylon film, silica vapor deposition stretched nylon film, alumina vapor deposition stretched nylon film, stretched polypropylene film, polyvinyl alcohol coated stretched polypropylene film, nylon 6 Or a metaxylylenediamine nylon 6 co-pushed co-stretched film or a polypropylene/ethylene-vinyl alcohol copolymer co-pushed co-stretched film, or a composite film in which two or more of these films are laminated.

Barrier Layer The laminate according to the present invention may further have a barrier layer. The barrier layer is made of an inorganic substance and/or an inorganic oxide, and is preferably made of a vapor deposition film of an inorganic substance or an inorganic oxide or a metal foil. The vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and forming method are not particularly limited. When the laminated body further includes the barrier layer, it is possible to impart or improve the gas barrier property of blocking transmission of oxygen gas, water vapor and the like and the light blocking property of blocking transmission of visible light and ultraviolet ray. The laminated body may have two or more barrier layers. When two or more barrier layers are provided, they may have the same composition or different compositions.

Examples of the vapor deposition film 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 other inorganic or inorganic oxide vapor deposition film can be used. In particular, as a material suitable for a packaging material (bag) or the like, it is preferable to use a vapor deposition film of aluminum metal, or a vapor deposition film of silicon oxide or aluminum metal or aluminum oxide.

The description of the inorganic oxide is, for example, MO _X (eg, SiO _X , AlO _X, etc., where M represents an inorganic element, and the value of X varies depending on the inorganic element). expressed. As the 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, 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 and 5, titanium (Ti). Is 0 to 2, lead (Pb) is 0 to 1, zirconium (Zr) is 0 to 2, and yttrium (Y) is 0 to 1.5. In the above, when X=0, the substance 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 preferably used for the packaging material, and 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. The value of can be used.

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

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 Examples thereof include chemical vapor deposition methods (Chemical Vapor Deposition method, CVD method) such as vapor phase growth method and photochemical vapor deposition method.

Moreover, according to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. As the metal foil, a conventionally known metal foil can be used. Aluminum foil and the like are preferable from the viewpoint of gas barrier properties that prevent the permeation of oxygen gas and water vapor and the like, and light shielding properties that prevent the permeation of visible light and ultraviolet light.

Paper Layer The laminate according to the present invention may further have a paper layer . Since the laminated body has the paper layer, it can have rigidity as a container. The paper used as the paper layer preferably has a basis weight of 10 to 150 g/m ² , and more preferably 20 to 100 g/m ² . As the paper layer, general "wrapping paper" of "Western paper" is targeted, but from the viewpoint of safety, it is preferable to use high-quality paper using 100% chemical pulp, art paper, or the like. Further, by having a paper layer derived from biomass such as natural pulp, the degree of biomass of the entire laminate can be improved, and an all-biomass laminate can also be realized.

Other Layers The laminate according to the present invention may further have at least one other layer in addition to the above layers. When two or more other layers are provided, they may have the same composition or different compositions. The other layer can be formed on any one of the above layers or two or more layers. Examples of the other layer include a printing layer and an adhesive layer. The printing layer can be formed using a conventionally known pigment or dye, and the forming method is not particularly limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed for laminating any two layers by laminating. As the adhesive for lamination, for example, one-component or two-component curing or non-curing vinyl type, (meth)acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, Other adhesives such as solvent type, aqueous type, emulsion type and the like can be used. As a method for coating the above-mentioned adhesive, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fonten method, a transfer roll coating method, or another method can be applied. As the coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry state) position are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry state) position is more preferred.

A resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, as the material of the adhesive resin layer, low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, and ethylene/α-olefin polymerized using a metallocene catalyst are used. Copolymer resin, ethylene/polypropylene copolymer resin, ethylene/vinyl acetate copolymer resin, ethylene/acrylic acid copolymer resin, ethylene/ethyl acrylate copolymer resin, ethylene/methacrylic acid copolymer resin, Ethylene/methyl methacrylate copolymer resin, ethylene/maleic acid copolymer resin, ionomer resin, polyolefin resin, unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, graft polymerization of ester monomer, Alternatively, a copolymerized resin, a resin obtained by graft-modifying maleic anhydride on a polyolefin resin, or the like can be used. These materials can be used alone or in combination of two or more.

The method for producing the laminate according to the present invention is not particularly limited, and the laminate can be produced by a conventionally known method. In the present invention, the biomass polyolefin resin layer is preferably formed by extrusion on the biomass polyester resin layer, and more preferably the biomass polyolefin resin layer is formed by coextrusion. It is further preferable that the coextrusion molding is performed by the T-die method or the inflation method.

For example, the laminate can be formed by extrusion molding by the following method. After drying the above-mentioned biomass polyolefin resin composition, it is supplied to a melt extruder heated to a temperature (Tm) higher than the melting point of polyolefin to Tm+70° C. to melt the biomass polyolefin resin composition, and the biomass polyester. A laminate can be formed by extruding the extruded sheet-like material onto the resin layer from a die such as a T-die, and rapidly solidifying the extruded sheet-like material with a rotating cooling drum or the like. As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

The thickness of the laminate obtained as described above is arbitrary depending on the application, but is usually about 5 to 500 μm, preferably about 20 to 300 μm.

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

Uses The laminate according to the present invention is used in various packaging products such as packaging containers and packaging bags, sheet molded products such as decorative sheets and trays, laminated films, optical films, resin plates, various label materials, lid materials, and laminated tubes. It can be preferably used for the intended use, and a packaging product is particularly preferable.

<Other aspects>
The present invention provides a laminate having a biomass polyester resin layer containing a carbon-neutral polyester using a biomass-derived ethylene glycol, and a biomass polyolefin resin layer containing a carbon-neutral polyolefin using a biomass-derived ethylene. Provided is a laminate having a polyester resin layer and a polyolefin resin layer produced from a raw material obtained from a conventional fossil fuel, and a laminate of a biomass resin that is comparable to physical properties such as mechanical properties. That is also the purpose.
According to yet another aspect of the invention,
A biomass polyester resin layer comprising a biomass polyester resin composition containing as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, wherein the diol unit is ethylene glycol derived from biomass,
Provided is a laminate comprising a biomass polyolefin resin layer made of a biomass polyolefin resin composition containing a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-containing monomer.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer.
In still another aspect of the present invention, the biomass polyolefin resin layer comprises a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side. Of the first biomass polyolefin resin layer contains 5% by mass or more of ethylene derived from the biomass, and the second biomass polyolefin resin layer contains the ethylene derived from the biomass in a second amount. It is preferably contained in an amount of 5% by mass or more based on the entire biomass polyolefin resin layer.
In yet another embodiment of the present invention, the biomass-derived ethylene concentration C ₁ in the first biomass polyolefin resin layer and the biomass-derived ethylene concentration C _{2 in} the second biomass polyolefin resin layer are C ₁ >C. It is preferable to satisfy ₂ .
In still another embodiment of the present invention, the monomer may further include fossil fuel-derived ethylene and/or α-olefin.
In still another aspect of the present invention, the monomer may further include a biomass-derived α-olefin.
In still another aspect of the present invention, the biomass polyolefin resin composition is derived from fossil fuel obtained by polymerizing a monomer containing ethylene derived from fossil fuel and ethylene and/or α-olefin derived from fossil fuel. It may further include a polyolefin.
In still another embodiment of the present invention, the biomass polyolefin resin composition may include 5 to 90% by mass of the biomass-derived polyolefin and 10 to 95% by mass of the fossil fuel-derived polyolefin.
In yet another aspect of the present invention, the α-olefin is preferably butylene, hexene, or octene.
In yet another aspect of the present invention, the polyolefin is preferably polyethylene.
In still another aspect of the present invention, the laminate may further include a non-biomass polyolefin resin layer made of a resin material containing a raw material derived from fossil fuel.
In still another aspect of the present invention, the laminate may further include a barrier layer made of an inorganic material and/or an inorganic oxide.
In yet another aspect of the present invention, the laminate may further include a paper layer.
In still another aspect of the present invention, it is preferable that the biomass polyolefin resin layer is formed on the biomass polyester resin layer by extrusion molding.
In still another aspect of the present invention, the biomass polyolefin resin layer is preferably formed by coextrusion molding.
In still another embodiment of the present invention, the coextrusion molding is preferably performed by a T die method or an inflation method.
In still another aspect of the present invention, there is provided a packaged product comprising the laminate.
A laminate according to still another aspect of the present invention is a biomass polyester resin layer containing a carbon-neutral polyester using a biomass-derived ethylene glycol, and a biomass polyolefin resin layer containing a carbon-neutral polyolefin using a biomass-derived ethylene. By having a laminated body including and, it is possible to realize a laminated body of carbon-neutral biomass resin. Therefore, it is possible to significantly reduce the amount of fossil fuel used as compared with the related art, and it is possible to reduce the environmental load. In addition, a laminate according to still another aspect of the present invention is comparable to a laminate of a resin produced from a raw material obtained from a conventional fossil fuel, in terms of physical properties such as mechanical properties. A resin laminate can be substituted.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Measurement/Conditions In the following Reference Examples, Reference Comparative Examples, Examples, and Comparative Examples, the biomass degree is the value of the content of carbon derived from biomass by the measurement of radioactive carbon (C14).

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

Preparation of resin film for core layer
Reference example 1
Biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 minutes) at a resin temperature of 290° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference example 2
50 parts by mass of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 min) and low fossil fuel-derived low A resin dry-blended with 50 parts by mass of density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) (biomass degree: 48% , Density: 0.937 g/cm ³ , MFR: 17 g/10 min) at a resin temperature of 290° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) to form a resin film. Obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference example 3
33 parts by mass of biomass-derived high-density polyethylene (manufactured by Braskem, trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g/cm ³ , MFR: 20 g/10 min), and low fossil fuel-derived low A resin dry-blended with 67 parts by mass of density polyethylene (manufactured by Nippon Polyethylene, trade name: LC701, biomass degree: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) (biomass degree: 32% , Density: 0.931 g/cm ³ , MFR: 16 g/10 min) at a resin temperature of 290° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) to form a resin film. Obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference Comparative Example 1
Fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, degree of biomass: 0%, density: 0.919 g/cm ³ , MFR: 14 g/10 minutes) at a resin temperature of 290° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Evaluation of Biomass Polyolefin Resin Composition and Resin Film Regarding the processability of the biomass polyolefin resin composition used in Reference Examples 1 to 3 and Reference Comparative Example 1 and the properties of the obtained film, the following various evaluations: (1) Drawdown, (2) neck-in, (3) motor load, (4) resin pressure, and (5) loop stiffness were performed.
(1) Drawdown The biomass polyolefin resin composition used in the above Reference Examples 1 to 3 and Reference Comparative Example 1 was subjected to T die width 560 mm, resin temperature 290° C., screw rotation speed using the above extrusion film forming machine. The maximum take-up speed (m/min) at which the extruded coating film was broken or surging was measured under the condition of 34 rpm. The measurement results were as shown in Table 1 below.

(2) Neck-in The biomass polyolefin resin compositions used in Reference Examples 1 to 3 and Reference Comparative Example 1 were subjected to a T die width of 560 mm and a screw rotation speed of 105 rpm using the above extrusion film forming machine. The binaural neck-in (mm) was measured at a take-up speed of 140 m/min and an air gap of 120 mm. The measurement results were as shown in Table 1 below.

(3) Motor Load In each of Reference Examples 1 to 3 and Reference Comparative Example 1 described above, the motor load (A) when the resin film was manufactured using the above extrusion film-forming machine was measured. The measurement results were as shown in Table 1 below.

(4) Resin Pressure In the above-mentioned Reference Examples 1 to 3 and Reference Comparative Example 1, the resin pressure (MPa) when the resin film was manufactured using the above extrusion film-forming machine was measured. The measurement results were as shown in Table 1 below.

(5) Loop Stiffness The resin films obtained in the above Reference Examples 1 to 3 and Reference Comparative Example 1 were cut into a width of 15 mm and a length of 150 mm, and subjected to a stiffness tester (trade name: Loop Stiffness manufactured by Toyo Seiki Seisakusho Co., Ltd.). The rigidity (N) of the film was measured using a tester. The length of the loop was 60 mm. The measurement results were as shown in Table 1 below.

Production of resin film for seal layer
Reference example 4
Biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 minutes) was added to a resin temperature of 320°C. Then, a 12 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) was extruded to obtain a resin film. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference example 5
33 parts by mass of linear low-density polyethylene derived from biomass (Blaskem: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and low fossil fuel-derived low 67 parts by mass of density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) was melt-blended (biomass degree: 29% , Density: 0.918 g/cm ³ , MFR: 6.3 g/10 min) at a resin temperature of 320° C. and extruded onto a PET film (manufactured by Toyobo Co., Ltd., trade name: E5100) having a thickness of 12 μm. I got a film. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference example 6
33 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and fossil fuel 37 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) and a straight chain derived from fossil fuel 30 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KC573, degree of biomass: 0%, density: 0.910 g/cm ³ , MFR: 15 g/10 minutes) was melt-blended (degree of biomass: 29 %, density: 0.916 g/cm ³ , MFR: 8.4 g/10 minutes) at a resin temperature of 320° C. onto a 12 μm-thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100), A resin film was obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference example 7
33 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g/cm ³ , MFR: 2.7 g/10 min), and fossil fuel 37 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC604, biomass degree: 0%, density: 0.918 g/cm ³ , MFR: 8 g/10 minutes) and a straight chain derived from fossil fuel 30 parts by mass of low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KS560T, biomass degree: 0%, density: 0.898 g/cm ³ , MFR: 16 g/10 minutes) was melt-blended (biomass degree: 29 %, density: 0.912 g/cm ³ , MFR: 8.7 g/10 minutes) at a resin temperature of 320° C. onto a 12 μm thick PET film (manufactured by Toyobo Co., Ltd., trade name: E5100), A resin film was obtained. The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Reference comparative example 2
Fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC600A, degree of biomass: 0%, density: 0.919 g/cm ³ , MFR: 7 g/10 minutes) at a resin temperature of 320° C. A resin film was obtained by extrusion onto a 12 μm PET film (manufactured by Toyobo Co., Ltd., trade name: E5100). The conditions of the extrusion molding were set such that the effective width was 560 mm, the extrusion thickness was 30 μm, and the extrusion speed was 100 m/min.

Evaluation of Biomass Polyolefin Resin Composition and Resin Film Regarding the processability of the biomass polyolefin resin composition used in Reference Examples 4 to 7 and Reference Comparative Example 2 described above and the characteristics of the obtained film, the following various evaluations: (6) Drawdown, (7) neck-in, (8) motor load, (9) resin pressure, and (10) seal start temperature were performed.

(6) Drawdown The biomass polyolefin resin compositions used in Reference Examples 4 to 7 and Reference Comparative Example 2 above were subjected to T-die width of 560 mm, resin temperature of 290° C., and screw rotation speed using the above extrusion film forming machine. The maximum take-up speed (m/min) at which the extruded coating film was broken or surging was measured under the condition of 34 rpm. The measurement results were as shown in Table 2 below.

(7) Neck-in The biomass polyolefin resin composition used in Reference Examples 4 to 7 and Reference Comparative Example 2 was subjected to T die width of 560 mm and screw rotation speed of 105 rpm by using the above extrusion film forming machine. The binaural neck-in (mm) was measured at a take-up speed of 140 m/min and an air gap of 120 mm. The measurement results were as shown in Table 2 below.

(8) Motor Load In each of Reference Examples 4 to 7 and Reference Comparative Example 2 described above, the motor load (A) when the resin film was manufactured using the extrusion film forming machine was measured. The measurement results were as shown in Table 2 below.

(9) Resin Pressure In the above-mentioned Reference Examples 4 to 7 and Reference Comparative Example 2, the resin pressure (MPa) when the resin film was manufactured using the above extrusion film-forming machine was measured. The measurement results were as shown in Table 2 below.

(10) Sealing start temperature The resin films obtained in Reference Examples 4 to 7 and Reference Comparative Example 2 were cut into a width of 15 mm and a length of 200 mm, the sealing temperature was 90 to 150°C, and the sealing pressure was 30 N/. The heat-sealing was performed at cm ² and a sealing time of 1 second. Using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.), this test piece was measured for peel strength at T at a tensile speed of 300 mm/min to specify the temperature (° C.) at which sealing was started. The measurement results were as shown in Table 2 below.

Example 1
Fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Corporation: LC701, MFR: 14, density: 0.919) and biomass-derived high-density polyethylene (manufactured by Braskem: SHA7260, MFR: 20, density: 0.955, biomass (Degree: 94.5%) and a dry blended resin of 50:50 was prepared. This resin was extrusion-coated on paper (pure white, basis weight 30 g/m ² ) to a thickness of 15 μm, and laminated on a biomass PET film (12 μm, biomass degree: 14%).

Next, as a core layer inside the biomass PET film (12 μm, biomass degree: 14%), low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: LC701, MFR: 14, density: 0.919) and biomass-derived A high-density polyethylene (manufactured by Braskem: SHA7260, MFR: 20, density: 0.955, biomass degree: 94.5%) was dry-blended at 50:50 to prepare a resin. Further, as the seal layer, a linear low-density polyethylene derived from fossil fuel (KC581, MFR: 11, density: 0.919 manufactured by Japan Polyethylene Co., Ltd.) and a linear low-density polyethylene derived from biomass (manufactured by Braskem: SLL318). , MFR: 2.7, density: 0.918, and biomass degree: 87%) were prepared by melt-blending at 67:33. The above resin was extrusion-coated by co-pressing (core layer: 15 μm, seal layer: 5 μm) at the resin temperature of 290° C. and 320° C. through the anchor coating agent on the inside of the biomass PET film to obtain a laminate. It was The biomass degree of the extruded layer was 44%. Using this laminated body, a pillow bag having an outer dimension of 20 mm×100 mm and a back seal width of 5 mm was prepared.

Comparative Example 1
Fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Corporation: LC701, MFR: 14, density: 0.919) was extrusion-coated on a paper (pure white, basis weight 30 g/m ² ) with a thickness of 15 μm, and a biomass PET film ( 12 μm, biomass degree: 14%).

Next, a low-density polyethylene derived from fossil fuel (manufactured by Japan Polyethylene Corporation: LC701, MFR: 14, density: 0.919) was prepared as a core layer inside the biomass PET film (12 μm, biomass degree: 14%). .. As the seal layer, a linear low-density polyethylene derived from fossil fuel (KC581, MFR:11, density: 0.919, manufactured by Nippon Polyethylene Co., Ltd.) was prepared. The above resin was extrusion-coated by co-pressing (core layer: 15 μm, seal layer: 5 μm) at a resin temperature of 290° C. and 320° C. through an anchor coating agent on the inside of the biomass PET film to obtain a laminate. It was The degree of biomass of the extruded layer was 0%. Using this laminated body, a pillow bag having an outer dimension of 20 mm×100 mm and a back seal width portion of 5 mm was prepared.

Each of the laminates obtained in Example 1 and Comparative Example 1 was cut into a piece having a width of 15 mm and a length of 200 mm, which was heat-sealed at a sealing temperature of 110 to 180° C., a sealing pressure of 30 N/cm ² , and a sealing time of 1 second. .. Using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.), this test piece was measured for peel strength at T at a tensile speed of 300 mm/min to identify the temperature at which sealing was started. The measurement results were as shown in Table 3 below.

Example 2
50 parts by mass of fossil fuel-derived low-density polyethylene (manufactured by Japan Polyethylene Corporation: LC701, MFR: 14, density: 0.955) and biomass-derived PET film (thickness 12 μm, biomass degree: 14%) A resin obtained by dry blending 50 parts by mass of linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) at 300° C. through an anchor coat. It was extruded at a resin temperature (15 μm) and attached to an aluminum foil (made by Nippon Foil Co., Ltd.: 1N30 material, thickness 7 μm). Furthermore, 50 parts by mass of fossil fuel-derived low-density polyethylene (LC701, MFR: 14, density: 0.955) derived from fossil fuel and linear low-density polyethylene derived from biomass (produced by Braskem: A resin dry-blended with 50 parts by mass of SLL318, MFR: 2.7, density: 0.918, biomass degree: 87% is extruded at a resin temperature of 300° C. through an anchor coat by an extrusion laminating method (30 μm). ), and the laminated body was obtained.

Comparative example 2
Fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Corporation: LC701, MFR: 14, density: 0.955) is applied to a biomass-derived PET film (thickness 12 μm, biomass degree: 14%) via an anchor coat. It was extruded (15 μm) at a resin temperature of 300° C. and laminated with an aluminum foil (manufactured by Japan Foil Co., Ltd.: 1N30 material, thickness 7 μm). Furthermore, fossil fuel-derived low-density polyethylene (LC701, MFR:14, density: 0.955 made by Japan Polyethylene Co., Ltd.) was extruded on the aluminum foil by an extrusion laminating method at a resin temperature of 300° C. via an anchor coat. It was extruded (30 μm) to obtain a laminate.

Each of the laminates obtained in Example 2 and Comparative Example 2 was cut out into a test piece with a width of 15 mm and a length of 200 mm. The PET film and the aluminum foil were peeled off, and the T-time peeling strength was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.). The tensile speed in this measurement was 50 mm/min. The measurement results were as shown in Table 4 below.

For each of the laminates obtained in Example 2 and Comparative Example 2, the test conditions were as follows except that the sealing pressure was 30 N/cm ² , the sealing time was 1 second, the sealing temperature was 170° C., and the pulling speed was 300 mm/min. The seal strength was measured under the same conditions as above. The measurement results were as shown in the table below.

Example 3
Aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and 12 μm thick biomass-derived PET film (TOYOBO Co., Ltd.: DE024, 12 μm) are dry-laminated (DIC: base material LX-) 703A/curing agent KR-90). Then, the PET film surface side was coated with a polyester polyol/isocyanate two-component curing type anchoring agent, and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923)). 320 parts of a resin obtained by dry blending 50 parts by mass of 50 parts by mass of a linear low-density polyethylene derived from biomass (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) While being extruded (20 μm, line speed 100 m/min) at a resin temperature of 0° C., a low density polyethylene film (manufactured by Dainippon Printing: SKL, density: 0.923, 40 μm) was attached to obtain a laminate. The biomass degree of the entire laminate was 10%.

Comparative Example 3
Aluminum foil (Toyo Aluminum Co., Ltd., 7 μm) and fossil fuel-derived PET film (Toyobo Co., Ltd.: E5100, 12 μm) are dry-laminated (DIC: main agent LX-703A/ It was pasted with a curing agent KR-90). Then, the PET film surface side was coated with a polyester polyol/isocyanate two-component curing type anchoring agent, and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Corporation: LC520 (MFR: 3.6, density: 0.923)). A resin obtained by dry-blending 50 parts by mass of 50 parts by mass of a linear low-density polyethylene derived from biomass (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) at 320° C. While being extruded (20 μm, line speed 100 m/min) at the resin temperature of No. 1, it was laminated with a low density polyethylene film (manufactured by Dainippon Printing: SKL, density: 0.923, 40 μm) to obtain a laminate. The biomass degree of the entire laminate was 7%.

10 Laminated body 11 Biomass polyester resin layer 12 Biomass polyolefin resin layer 20 Laminated body 21 Biomass polyester resin layer 22 First biomass polyolefin resin layer 23 Second biomass polyolefin resin layer

Claims (7)

A biomass polyester resin composition comprising a polyester comprising a diol unit and a dicarboxylic acid unit as a main component, wherein the diol unit is a biomass-derived ethylene glycol, or a fossil fuel-derived diol unit. A fossil fuel polyester resin layer comprising a fossil fuel polyester resin composition containing as a main component a polyester comprising a fossil fuel-derived dicarboxylic acid unit, and
Low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, linear low density polyethylene resin, copolymer resin with ethylene/α-olefin polymerized using metallocene catalyst, ethylene/polypropylene copolymer resin, Ethylene/vinyl acetate copolymer resin, ethylene/acrylic acid copolymer resin, ethylene/ethyl acrylate copolymer resin, ethylene/methacrylic acid copolymer resin, ethylene/methyl methacrylate copolymer resin, ethylene/malein Acid copolymer resin, ionomer resin, polyolefin resin, unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, graft polymerization of ester monomers, or copolymerized resin, maleic anhydride polyolefin resin An adhesive resin layer containing one or more selected from the group consisting of resins graft-modified with
A barrier layer containing an inorganic material,
A biomass polyolefin resin layer made of a biomass polyolefin resin composition containing biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene, and having in this order,
A laminate in which the density of the biomass polyolefin resin layer is 0.90 to 0.925 g/cm ³ . The laminate according to claim 1, wherein the biomass polyolefin resin layer comprises low density polyethylene derived from biomass and/or linear low density polyethylene derived from biomass. The laminate according to claim 1 or 2, wherein the biomass polyolefin resin layer comprises low density polyethylene and linear low density polyethylene. The layered product according to any one of claims 1 to 3, wherein the biomass polyolefin resin layer contains 5% by mass or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer. The laminate according to any one of claims 1 to 4, wherein the barrier layer is made of a metal foil. The polyester resin layer is Ru the biomass polyester resin layer der laminate according to any one of claims 1-5. A packaged product comprising the laminate according to any one of claims 1 to 6.

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