JP6443769B2 - Laminate with a resin layer derived from biomass - Google Patents

Description

  The present invention relates to a laminate comprising a biomass-derived resin layer, and more specifically, a biomass polyester resin layer comprising a biomass polyester whose diol unit is biomass-derived ethylene glycol, and a monomer containing biomass-derived ethylene. The present invention relates to a laminate comprising a biomass polyolefin resin layer comprising a biomass-derived polyolefin formed by polymerizing.

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

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

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

  Therefore, it is desired to reduce the amount of fossil fuel used by using raw materials derived from biomass for the production of polyethylene. For example, until now, it has been studied to produce ethylene and butylene as raw materials for polyolefin resin from renewable natural raw materials (see, for example, Patent Document 1).

Special table 2011-506628 gazette

  The inventors focused on ethylene, which is a raw material for polyolefin laminates, and instead of ethylene obtained from conventional fossil fuels, a laminate having a polyolefin polyolefin polyolefin resin layer of polyolefin using biomass-derived ethylene as its raw material is The present inventors have obtained the knowledge that a laminate of polyolefin resin produced using ethylene obtained from a conventional fossil fuel and a product inferior in physical properties such as mechanical properties can be obtained. The present invention is based on this finding.

Accordingly, an object of the present invention includes a biomass polyester resin layer containing a carbon neutral polyester using biomass-derived ethylene glycol, a biomass polyolefin resin layer containing a carbon-neutral polyolefin using biomass-derived ethylene, and an inorganic substance. A laminate comprising a barrier layer and a heat seal layer having a density of 0.90 to 0.925 g / cm ³ , wherein the biomass polyolefin resin layer is located between the biomass polyester resin layer and the barrier layer A laminate having a polyester resin layer and a polyolefin resin layer manufactured from a raw material obtained from a conventional fossil fuel, and a biomass resin laminate that is inferior in terms of physical properties such as mechanical properties. Is to provide.

In an embodiment of the present invention,
A biomass polyester resin layer comprising a biomass polyester resin composition comprising as a main component a polyester comprising a diol unit and a dicarboxylic acid unit, wherein the diol unit is biomass-derived ethylene glycol,
Biomass-derived polyethylene obtained by polymerizing monomers containing ethylene derived from biomass, and fossil fuel-derived polyethylene obtained by polymerizing ethylene derived from fossil fuel and ethylene derived from fossil fuel and / or α-olefin monomer. A biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising;
A barrier layer containing an inorganic substance;
A heat seal layer having a density of 0.90 to 0.925 g / cm ³ ;
Having
There is provided a laminate in which the biomass polyolefin resin layer is located between the biomass polyester resin layer and the barrier layer.

  In the aspect of this invention, it is preferable that the said biomass polyolefin resin layer contains 5 mass% or more of said biomass-derived ethylene with respect to the said biomass polyolefin resin layer whole.

  In an aspect of the present invention, the biomass polyolefin resin layer includes a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side, and the first biomass polyolefin resin The layer comprises 5 mass% or more of the biomass-derived ethylene with respect to the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains the biomass-derived ethylene in the second biomass polyolefin resin layer. It is preferable to contain 5 mass% or more with respect to the whole.

In the 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 satisfy C ₁ > C _2. Is preferred.

In the aspect of the present invention, the monomer containing ethylene derived from biomass may further contain ethylene derived from fossil fuel and / or α-olefin.

In the aspect of the present invention, the monomer containing ethylene derived from biomass may further contain ethylene derived from fossil fuel and / or α-olefin.

In the aspect of the present invention, the biomass polyolefin resin composition may include 5 to 90% by mass of the polyethylene derived from the biomass and 10 to 95% by mass of the polyethylene derived from the fossil fuel.

  In the aspect of the present invention, the α-olefin is preferably butylene, hexene, or octene.

  In the aspect of the present invention, the laminate may further include a non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived raw material.

  In the aspect of the present invention, the laminate may further include a paper layer.

In another aspect of the present invention, there is provided a method for producing a laminate, which is bonded to the barrier layer while extruding the biomass polyolefin resin layer.

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

The laminate according to the present invention includes a biomass polyester resin layer containing carbon neutral polyester using biomass-derived ethylene glycol, a biomass polyolefin resin layer containing carbon neutral polyolefin using biomass-derived ethylene, and a barrier containing an inorganic substance. Layer and a heat seal layer having a density of 0.90 to 0.925 g / cm ³ , and a laminate in which the biomass polyolefin resin layer is located between the biomass polyester resin layer and the barrier layer It is possible to realize a carbon neutral biomass resin laminate. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, and the environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a resin laminate manufactured from a raw material obtained from a conventional fossil fuel. 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, “biomass polyester resin composition”, “biomass polyester resin layer”, “biomass polyolefin resin composition”, and “biomass polyolefin resin layer” used a raw material derived from biomass at least in part as a raw material. It does not mean that all the raw materials are derived from biomass.

Laminated body The laminated body by this invention has a biomass polyester resin layer and a biomass polyolefin resin layer. By having a biomass polyolefin resin layer, the laminate can realize a laminate of a carbon neutral polyolefin resin. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, and the environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a polyolefin resin laminate produced from a raw material obtained from a conventional fossil fuel. Can be substituted.

  A schematic cross-sectional view of an example of a laminate according to the present invention is shown in FIGS. A laminate 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 was 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 which comprises a laminated body is demonstrated.

Biomass polyester resin layer In this invention, a biomass polyester resin layer consists of the following biomass polyester resin composition which contains the polyester which consists of a diol unit and a dicarboxylic acid unit as a main component.

Biomass polyester The biomass polyester contained in the biomass polyester resin composition is composed of 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 a fossil fuel-derived dicarboxylic acid.

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

  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 acid, aliphatic dicarboxylic acid, and derivatives thereof can be used without limitation. Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid, and examples of the aromatic dicarboxylic acid derivative include lower alkyl esters of aromatic dicarboxylic acid, specifically methyl ester, ethyl ester, propyl ester, and butyl. Examples include esters. Among these, terephthalic acid is preferable, and dimethyl terephthalate is preferable as an aromatic dicarboxylic acid derivative.

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

  These dicarboxylic acids can be used alone or in combination of two or more.

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

  Further, the biomass polyester may be a high molecular weight biomass polyester obtained by chain extending (coupling) these copolymerized biomass polyesters. Chain extenders such as carbonate compounds and diisocyanate compounds can also be used as chain extenders, but the amount is usually carbonate bonds and urethane bonds relative to 100 mol% of all monomer units constituting the biomass polyester. 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, and dicyclohexyl. Examples include carbonate. 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 range isocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate can be used.

  Biomass polyester can be obtained by a conventionally known method in which the above-described diol unit and dicarboxylic acid unit are polycondensed. Specifically, after performing the esterification reaction and / or transesterification reaction of the dicarboxylic acid component and the diol component, a general method of melt polymerization such as a polycondensation reaction under reduced pressure, or an organic solvent It can be produced by a known solution heating dehydration condensation method using

  The amount of the diol used when producing the biomass polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof. Generally, however, esterification and / or transesterification and / or polycondensation reactions are performed. It is used in an excess of 0.1 to 20 mol% because there is a distillation inside.

  The polycondensation reaction is preferably performed in the presence of a polymerization catalyst. The addition timing of the polymerization catalyst is not particularly limited as long as it is before the polycondensation reaction, and it may be added when the raw materials are charged, or may be added at the start of pressure reduction.

  Examples of the polymerization catalyst include compounds containing a Group 1 to Group 14 metal element excluding hydrogen and carbon in the periodic table. 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. And compounds containing an organic group such as carboxylate, alkoxy salt, organic sulfonate, or β-diketonate salt, and inorganic compounds such as metal oxides and halides described above, and mixtures thereof. Of these, metal compounds containing titanium, zirconium, germanium, zinc, aluminum, magnesium and calcium, and mixtures thereof are preferred, and titanium compounds, zirconium compounds and germanium compounds are particularly preferred. In addition, the catalyst is preferably a compound that is liquid at the time of polymerization or that dissolves in an ester low polymer or biomass polyester, because the polymerization rate increases when it is melted or dissolved at the time of polymerization.

  The titanium compound is preferably a tetraalkyl titanate, specifically, tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples include benzyl titanate and mixed titanates thereof. In addition, 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 triethanolamate, butyl titanate dimer and the like are also preferably used. Furthermore, titanium oxide and composite oxides containing titanium and silicon are 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), particularly tetra-n-butyl titanate, polyhydroxy titanium stearate , Titanium (oxy) acetylacetonate, titanium tetraacetylacetonate, titania / silica composite oxide (for example, Acordis Industrial Fiber) The product name manufactured by s company: C-94) is preferable.

  Specific examples of the zirconium compound include zirconium tetraacetate, zirconium acetylate hydroxide, zirconium tris (butoxy) stearate, zirconyl diacetate, zirconium oxalate, zirconyl oxalate, potassium potassium oxalate, and polyhydroxyzirconium. Examples include stearate, zirconium ethoxide, zirconium tetra-n-propoxide, zirconium tetraisopropoxide, zirconium tetra-n-butoxide, zirconium tetra-t-butoxide, zirconium tributoxyacetylacetonate and mixtures thereof. Further, zirconium oxide or a complex oxide containing, for example, zirconium and silicon may be used. Among these, zirconyl diacetate, zirconium tris (butoxy) stearate, zirconium tetraacetate, zirconium acetate acetate, zirconium ammonium oxalate, potassium potassium oxalate, polyhydroxyzirconium stearate, zirconium tetra-n-propoxy Zirconium tetraisopropoxide, zirconium tetra-n-butoxide, and zirconium tetra-t-butoxide are preferred.

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

  The amount of the catalyst used in the case of using a metal compound as the polymerization catalyst, the lower limit is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30000 ppm or less, preferably 1000 ppm or less as the amount of metal to the biomass polyester to be produced. More preferably, it is 250 ppm or less, and particularly preferably 130 ppm or less. If too much catalyst is used, it is not only economically disadvantageous but also lowers the thermal stability of the polymer. Conversely, if it is too little, the polymerization activity is lowered, and as a result, the polymer decomposes during polymer production. Is more likely to be triggered. As the amount of catalyst used here, the amount of the terminal carboxyl group of the biomass polyester to be generated is reduced as the amount of use is reduced, so the method of reducing the amount of catalyst used is a preferred embodiment.

  The reaction temperature of the esterification reaction and / or transesterification reaction between 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. . Further, the reaction pressure is usually normal pressure to 10 kPa. The reaction time is usually about 1 hour to 10 hours.

In the production process described above, a chain extender (coupling agent) may be added to the reaction system.
After the end 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.

  High molecular weight biomass polyesters using these chain extenders (coupling agents) can be produced using known techniques. 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. Specifically, biomass obtained by catalyzing a diol and a dicarboxylic acid, having a terminal group substantially having a hydroxyl group, and having a mass average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. A biomass polyester resin having a higher molecular weight can be obtained by reacting the polyester prepolymer with the chain extender. If the prepolymer has a mass average molecular weight of 20,000 or more, the use of a small amount of a coupling agent does not affect the remaining catalyst even under severe conditions such as a molten state, so that no gel is formed during the reaction. A high molecular weight biomass polyester can be produced.

After the obtained biomass polyester is solidified, solid phase polymerization may be performed as necessary in order to further increase the degree of polymerization or remove oligomers such as cyclic trimers.
Specifically, after biomass polyester is chipped and dried, 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 for 1 to several tens of hours under inert gas flow or reduced pressure.

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

  Various additives may be added to the biomass polyester in the manufacturing process of the biomass polyester or the manufactured biomass polyester as long as the characteristics are not impaired. For example, plasticizer, UV stabilizer, anti-coloring agent, gloss Detergents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, ion exchange agents, color pigments, 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 with respect to the whole biomass polyester resin composition.

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

  As the resin that is the basis of the recycled polyester (that is, the polyester resin before recycling), the diol unit and the dicarboxylic acid unit are both made of a fossil fuel-derived raw material (non-biomass polyester) as described above. Biomass polyester may be sufficient.

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

The biomass polyester resin composition containing the biomass polyester obtained as described above contains 10 to 19% of the carbon derived from biomass as measured by radioactive carbon (C14) with respect to the total carbon in the biomass polyester. Is preferred. Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, 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, the biomass-derived carbon content P _bio when the _C14 content in the biomass polyester is PC ₁₄ is defined as follows.
P _bio (%) = P _C14 /105.5×100

Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymer obtained by polymerizing ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1: 1. Is used, the content P _bio of carbon derived from biomass in the biomass polyester is 20%.
In this invention, it is preferable that content of the carbon derived from biomass by a radioactive carbon (C14) measurement is 10 to 19% with respect to the total carbon in a biomass polyester resin composition. When the carbon content derived from biomass 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 biomass-derived carbon content in the biomass polyester resin composition is preferably closer to 20%, but from the viewpoint of problems in film production processes 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-described biomass polyester resin composition. In order to process the biomass polyester resin composition into a film, a method of forming a film from a conventional polyester resin can be employed. Specifically, after drying the above-described biomass polyester resin composition, the biomass polyester resin composition is supplied to a melt extruder heated to a temperature not lower than the melting point of the biomass polyester (Tm) to Tm + 70 ° C. The film can be formed by, for example, extruding into a sheet from a die such as a T-die, and rapidly cooling and solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

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

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

  Although heat setting is subsequently performed after the transverse stretching, a preferable temperature range of heat setting is Tg + 70 to Tm-10 ° C. of biomass polyester. The heat setting time is preferably 1 to 60 seconds. Furthermore, for applications that require a low thermal shrinkage rate, heat relaxation treatment may be performed as necessary.

In the resin film obtained as described above, the thickness of the stretched film 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 from 50 to 350% in MD direction, the TD direction 50-300%. Further, the shrinkage rate when left in a temperature environment of 150 ° C. for 30 minutes is 0.1 to 5%. Thus, the biomass polyester resin film used as the biomass resin layer of the laminate according to the present invention is equivalent to the physical properties of a polyester resin film produced only from a conventional fossil fuel-derived material.

Biomass polyolefin resin layer In the present invention, the biomass polyolefin resin layer is preferably 5% by mass or more, more preferably 5 to 95% by mass, more preferably 25 to 95% by mass of the following biomass-derived ethylene with respect to the entire biomass polyolefin resin layer. It contains 75% by mass. The biomass polyolefin resin layer may be composed of at least two layers. For example, the biomass polyolefin resin layer includes a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side. Both the sealing 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.

1st biomass polyolefin resin layer In this invention, the 1st biomass polyolefin resin layer may fulfill | perform the function as a core layer of a laminated body. By having the core layer, the laminate can exhibit excellent flexibility without breaking.

  The first biomass polyolefin resin layer is preferably 5% by mass or more, more preferably 5 to 95% by mass, more preferably 25 to 75% by mass, of ethylene derived from biomass with respect to the entire first biomass polyolefin resin layer. Most preferably, it comprises 40 to 75%. If the concentration of ethylene derived from biomass 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, 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 defined in Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. When 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. Moreover, if the first biomass polyolefin resin layer density 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 method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. If the MFR of the first biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if MFR of a biomass polyolefin resin composition is 30 g / 10min or less, the mechanical strength of a 1st biomass polyolefin resin layer can be raised.

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

2nd biomass polyolefin resin layer In this invention, the 2nd biomass polyolefin resin layer may fulfill | perform the function as a sealing layer of a laminated body. By having the heat seal layer, the laminate can be firmly bonded without using an adhesive or the like when laminating on another resin film.

  The second 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, and even more preferably 25 to 75% by mass with respect to the entire second biomass polyolefin resin layer. It is what. If the concentration of ethylene derived from biomass 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 one, 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 Method A of JIS K7112-1980 after annealing described in JIS K6760-1995. If 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 a 2nd biomass polyolefin resin layer is 0.925 g / cm < ³ > or less, transparency and mechanical strength of a 2nd biomass polyolefin resin layer can be improved.

  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 method A under the conditions of a temperature of 190 ° C. and a load of 21.18 N in the method defined in JIS K7210-1995. If the MFR of the second biomass polyolefin resin layer is 1 g / 10 min or more, the extrusion load during the molding process can be reduced. Moreover, if the MFR of the biomass polyolefin resin composition is 30 g / 10 min 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 relationship regarding density, thickness, MFR, and biomass degree (ethylene concentration derived from biomass). Preferably there is.

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 and therefore requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and thus requires flexibility.

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 therefore requires a thickness, and the second biomass polyolefin resin layer functions as a heat seal layer, so that the thickness is not as large 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 and therefore requires rigidity, and the second biomass polyolefin resin layer functions as a heat seal layer and thus requires flexibility.

In the present invention, the first ethylene concentration C ₁ of biomass-derived biomass polyolefin resin layer and the second ethylene concentration C ₂ of the biomass-derived biomass polyolefin resin layer, it is preferable to satisfy the C _1> C _2. Since the first biomass polyolefin resin layer functions as a core layer, since the thickness is large and the amount of ethylene used is large, the amount of fossil fuel used can be further reduced by increasing the biomass degree of the first biomass polyolefin resin layer. It is.

Biomass-derived ethylene In the present invention, a method for producing biomass-derived ethylene that is a raw material for biomass-derived polyolefin is not particularly limited, and can be obtained by a conventionally known method. Hereinafter, an example of a method for producing biomass-derived ethylene 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. A plant raw material is not specifically limited, A conventionally well-known plant can be used. For example, corn, sugar cane, beet, and manioc can be mentioned.

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

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

  When ethylene is obtained by a dehydration reaction of ethanol, a catalyst is usually used, but this catalyst is not particularly limited, and a conventionally known catalyst can be used. Advantageous in the process is a fixed bed flow reaction in which the catalyst and the product can be easily separated. For example, γ-alumina is preferable.

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

  The reaction pressure is not particularly limited, but a pressure equal to or higher than normal pressure is preferable in order to facilitate subsequent gas-liquid separation. Industrially, a fixed bed flow reaction in which separation of the catalyst is easy is suitable, 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. Generally, when performing a dehydration reaction, it is preferable that there is no water in view of water removal efficiency. However, in the case of ethanol dehydration reaction using a solid catalyst, it has been found that in the absence of water, the production of other olefins, particularly butene, tends to increase. It is presumed that ethylene dimerization after dehydration cannot be suppressed unless a small amount of water is present. The lower limit of the allowable water content is 0.1% or more, preferably 0.5% or more. Although an upper limit is not specifically limited, From a viewpoint of a mass balance and a heat balance, Preferably it is 50 mass% or less, More preferably, it is 30% or less, More preferably, it is 20% or less.

  By performing a 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 a temperature of about 5 MPa or less at normal temperature, gas and liquid separation from these mixed parts Ethylene can be obtained except water and ethanol. This method may be performed by a known method.

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

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

  In addition, you may use caustic water treatment together as a refinement | purification method of the impurity in ethylene. In the case of performing caustic water treatment, 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, biomass-derived polyolefin is obtained by polymerizing monomers containing ethylene derived from biomass. It is preferable to use what was obtained by said manufacturing method for ethylene derived from biomass. Since ethylene derived from biomass is used as a monomer as a raw material, the polymerized polyolefin is derived from biomass.
In addition, the raw material monomer of polyolefin does not need to contain 100 mass% of ethylene derived from biomass.

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

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

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

The biomass-derived ethylene concentration in the polyolefin (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the content of biomass-derived carbon by measurement of radioactive carbon (C14). Since carbon dioxide in the atmosphere contains C14 at a constant ratio (105.5 pMC), the C14 content in plants that grow by incorporating carbon dioxide in the atmosphere, for example, 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, in the case where the content of C14 in the polyolefin was P _C14, the content P _{bio Bio} carbon from biomass, can be obtained as follows.
P _bio (%) = P _C14 /105.5×100

  In the present invention, theoretically, if all the biomass-derived ethylene is used as the polyolefin raw material, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyolefin is 100%. In addition, the biomass-derived ethylene concentration 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 and 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 laminate, the amount of the fossil fuel used is reduced as compared with the conventional case.

  In the present invention, the polymerization method of the monomer containing ethylene derived from biomass is not particularly limited, and can be performed by a conventionally known method. The polymerization temperature and polymerization pressure are preferably adjusted as appropriate according to the polymerization method and polymerization apparatus. The polymerization apparatus is not particularly limited, and a conventionally known apparatus can be used. Hereinafter, an example of a method for polymerizing a monomer containing ethylene will be described.

The polymerization method of polyolefins, particularly ethylene polymers and copolymers of ethylene and α-olefins, is the type of polyethylene of interest, such as high density polyethylene (HDPE), medium density polyethylene (MDPE), and low density polyethylene (LDPE). ), And linear low density polyethylene (LLDPE), etc.
For example, as a polymerization catalyst, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single site catalyst such as a metallocene catalyst, by any of gas phase polymerization, slurry polymerization, solution polymerization, and high-pressure ion polymerization, It is preferable to carry out by one stage or two or more stages.

  The above single-site catalyst is a catalyst that can form a uniform active species, and is usually adjusted by bringing a metallocene transition metal compound or a nonmetallocene transition metal compound into contact with an activation cocatalyst. . The single site catalyst is preferable because the active site structure is uniform as compared with the multisite catalyst, and a polymer having a high molecular weight and a high degree of uniformity can be polymerized. As the single site catalyst, it is particularly preferable to use a metallocene catalyst. The metallocene-based catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a cocatalyst, and if necessary, an organometallic compound, and each catalyst component of the support. is there.

  In the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, or the like. . Examples of substituted cyclopentadienyl groups include hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl substituted alkyl groups, silyl substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups. It has at least one kind of substituent selected from a group 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, etc. It may be formed. Rings formed by bonding substituents to each other may further have substituents.

  In the group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, hafnium, and zirconium and hafnium are particularly preferable. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and each ligand having a cyclopentadienyl skeleton is preferably bonded to each other via a bridging group. Examples of the crosslinking group include substituted alkylene groups such as C1-C4 alkylene groups, silylene groups, dialkylsilylene groups, and diarylsilylene groups, dialkylgermylene groups, and diarylgermylene groups. Preferably, it is a substituted silylene group.

  In the transition metal compound of Group IV of the periodic table, as a ligand other than a ligand having a cyclopentadienyl skeleton, hydrogen, a hydrocarbon group having 1 to 20 carbon atoms (an alkyl group) is typical. Alkenyl group, aryl group, alkylaryl group, aralkyl group, polyenyl group, etc.), halogen, metaalkyl group, metaaryl group and the like.

  The transition metal compound of Group IV of the Periodic Table containing a ligand having a cyclopentadienyl skeleton can use one or a mixture of two or more as a catalyst component.

  The co-catalyst is one that can effectively make the above-mentioned group IV transition metal compound as a polymerization catalyst, or can neutralize ionic charges in a catalytically activated state. Co-catalysts include benzene-soluble aluminoxanes of organoaluminum oxy compounds, benzene-insoluble organoaluminum oxy compounds, ion-exchange layered silicates, boron compounds, active hydrogen group-containing or non-containing cations and non-coordinating anions. Ionic compounds, lanthanoid salts such as lanthanum oxide, tin oxide, phenoxy compounds containing a fluoro group, and the like.

The group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound carrier. The support is preferably a porous oxide of an inorganic or organic compound. 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.

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

  Further, as the polyolefin, an ethylene polymer or an ethylene / α-olefin copolymer may be used alone or in combination of two or more.

Biomass polyolefin resin composition In this invention, a biomass polyolefin resin composition contains said polyolefin as a main component. The biomass polyolefin resin composition preferably comprises 5 mass% or more, more preferably 5 to 95 mass%, still more preferably 25 to 75 mass%, of ethylene derived from biomass with respect to the entire biomass polyolefin resin composition. is there. If the concentration of ethylene derived from biomass 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 one, and a carbon neutral polyolefin laminate can be realized.

  The biomass polyolefin resin composition may contain two or more kinds of polyolefins having different biomass degrees, 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 ethylene derived from fossil fuel and ethylene derived from fossil fuel and / or α-olefin. That is, in the present invention, the biomass polyolefin resin composition may be a mixture of biomass-derived polyolefin and fossil fuel-derived polyolefin. The mixing method is not particularly limited, and mixing can be performed by a conventionally known method. For example, a dry blend or a melt blend may be used.

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

  In the production process of the above-described biomass polyolefin resin composition, or in the produced biomass polyolefin resin composition, various additives other than the main component polyolefin may be added as long as the characteristics are not impaired. Good. Examples of additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, slip agents, mold release agents, An oxidizing agent, an ion exchange agent, a coloring pigment, and the like can be added. These additives are preferably added in an amount of 1 to 20% by mass, preferably 1 to 10% by mass, based on the whole 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 a conventionally known raw material, and the composition and formation method thereof are not particularly limited. When the laminate further has a 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 having two or more non-biomass polyolefin resin layers, each may have the same composition or a different composition.

  Non-biomass polyolefin resin layers include, for example, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid. A resin such as a copolymer, an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, or an ionomer can be used. These resins may be formed by an extrusion laminating method, or may be laminated in advance as a film formed by a T-die method or an inflation method by a heat-resistant substrate layer and a dry laminating or extrusion laminating method. .

  Also, stretched polyethylene terephthalate film, silica-deposited stretched polyethylene terephthalate film, alumina-deposited stretched polyethylene terephthalate film, stretched nylon film, silica-deposited stretched nylon film, alumina-deposited stretched nylon film, stretched polypropylene film, polyvinyl alcohol-coated stretched polypropylene film, nylon 6 / Metaxylylenediamine nylon 6 co-extrusion co-stretched film or polypropylene / ethylene-vinyl alcohol copolymer co-extrusion co-stretched film or the like, or a composite film obtained by laminating two or more of these films may be used.

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

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

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

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

  As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

  According to another aspect, the barrier layer may be a metal foil obtained by rolling a metal. A conventionally known metal foil can be used as the metal foil. Aluminum foil or the like is preferable from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.

Paper Layer The laminate according to the present invention may further have a paper layer . When the laminate has a 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 , more preferably 20 to 100 g / m ² . As the paper layer, “wrapping paper” of “medium paper” in general is an object, but from the viewpoint of safety, the use of high-quality paper using 100% chemical pulp, art paper or the like is preferable. Moreover, the biomass degree of the whole laminated body can be improved by having a paper layer derived from biomass, such as natural pulp, and the laminated body of all biomass can also be implement | achieved.

Other Layers In addition to the above layers, the laminate according to the present invention may further include at least one other layer. When two or more other layers are included, each may have the same composition or a different composition. Other layers can be formed on any one or more of the above layers. Examples of other layers include a printing layer and an adhesive layer. A printing layer can be formed using a conventionally well-known pigment and dye, The formation method is not specifically limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed in order to bond any two layers by lamination. As an adhesive for laminating, for example, one or two-component cured or non-cured 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, and emulsion type can be used. Examples of the coating method for the adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods. 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.

  In addition, a resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, the material of the adhesive resin layer includes a low density polyethylene resin, a medium density polyethylene resin, a high density polyethylene resin, a linear low density polyethylene resin, and ethylene / α-olefin polymerized using a metallocene catalyst. 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, Graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester monomer to ethylene / methyl methacrylate copolymer resin, ethylene / maleic acid copolymer resin, ionomer resin, polyolefin resin, Or graft copolymerized resin, maleic anhydride to polyolefin resin It can be used sexual resin or the like. These materials can be used alone or in combination.

  The manufacturing method of the laminated body by this invention is not specifically limited, It can manufacture by a conventionally well-known method. In the present invention, it is preferable to form a biomass polyolefin resin layer on the biomass polyester resin layer by extrusion molding, and it is more preferable that the biomass polyolefin resin layer is formed by coextrusion molding. More preferably, the coextrusion is performed by a T-die method or an inflation method.

  For example, the laminate can be formed by extrusion molding according to the following method. After drying the above-described biomass polyolefin resin composition, the biomass polyolefin resin composition is melted by supplying it to a melt extruder heated to a temperature not lower than the melting point (Tm) to Tm + 70 ° C. of the polyolefin, and biomass polyester. A laminated body can be formed by extruding the resin layer on a resin layer, for example, from a die such as a T die, and rapidly solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

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

Applications Laminates according to the present invention are packaged 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 used suitably for a use, and a package product is particularly preferable.
Other aspects
The present invention provides a laminate comprising a biomass polyester resin layer containing carbon neutral polyester using biomass-derived ethylene glycol, and a biomass polyolefin resin layer containing carbon-neutral polyolefin using biomass-derived ethylene. The present invention provides a laminate having a polyester resin layer and a polyolefin resin layer manufactured from a raw material obtained from a conventional fossil fuel, and a biomass resin laminate that is inferior in terms of physical properties such as mechanical properties. Also aimed.
According to yet another aspect of the invention,
A biomass polyester resin layer comprising a biomass polyester resin composition comprising as a main component a polyester comprising a diol unit and a dicarboxylic acid unit, wherein the diol unit is biomass-derived ethylene glycol,
A biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising a biomass-derived polyolefin obtained by polymerizing a monomer containing ethylene derived from biomass;
A laminate comprising: is provided.
In the aspect of the present invention, the biomass polyolefin resin layer may include 5 mass% or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer.
In an aspect of the present invention, the biomass polyolefin resin layer includes a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side, and the first biomass polyolefin resin The layer comprises 5 mass% or more of the biomass-derived ethylene with respect to the entire first biomass polyolefin resin layer, and the second biomass polyolefin resin layer contains the biomass-derived ethylene in the second biomass polyolefin resin layer. You may contain 5 mass% or more with respect to the whole.
In embodiments of the present invention, the first ethylene concentration C ₁ of biomass-derived biomass polyolefin resin layer of the biomass of the second biomass polyolefin resin layer is ethylene concentration C _2, satisfies C _1> C ₂ Also good.
In an embodiment of the present invention, the monomer may further contain ethylene and / or α-olefin derived from fossil fuel.
In the aspect of the present invention, the monomer may further contain an α-olefin derived from biomass.
In an aspect of the present invention, the biomass polyolefin resin composition further includes a fossil fuel-derived polyolefin obtained by polymerizing a fossil fuel-derived ethylene and a fossil-fuel-derived ethylene and / or α-olefin monomer. But you can.
In the aspect 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 the embodiment of the present invention, the α-olefin may be butylene, hexene, or octene.
In the embodiment of the present invention, the polyolefin may be polyethylene.
In the aspect of the present invention, the laminate may further include a non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived raw material.
In the aspect of this invention, the said laminated body may further have a barrier layer which consists of an inorganic substance and / or an inorganic oxide.
In the aspect of the present invention, the laminate may further include a paper layer.
In the aspect of the present invention, the biomass polyolefin resin layer may be formed on the biomass polyester resin layer by extrusion molding.
In the aspect of the present invention, the biomass polyolefin resin layer may be formed by coextrusion molding.
In the aspect of the present invention, the coextrusion molding may be performed by a T-die method or an inflation method.
In another aspect of the present invention, a packaged product comprising the laminate is provided.
Such a laminate according to the present invention has a biomass polyester resin layer containing carbon-neutral polyester using biomass-derived ethylene glycol, and a biomass polyolefin resin layer containing carbon-neutral polyolefin using biomass-derived ethylene. By having the laminated body formed as described above, a carbon-neutral biomass resin laminated body can be realized. Therefore, the amount of fossil fuel used can be greatly reduced compared to the conventional case, and the environmental load can be reduced. In addition, the laminate according to the present invention is not inferior in terms of physical properties such as mechanical properties as compared with a resin laminate manufactured from a raw material obtained from a conventional fossil fuel. can do.

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

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 as measured by radioactive carbon (C14).

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

Production 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 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 Resin obtained by dry blending 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 min) (biomass degree: 48%) , Density: 0.937 g / cm ³ , MFR: 17 g / 10 min) at a resin temperature of 290 ° C., and extruded onto a 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.). Obtained.
The conditions for 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 (trade name: SHA7260, biomass degree: 94.5%, density: 0.955 g / cm ³ , MFR: 20 g / 10 min, manufactured by Braskem), low from fossil fuel Resin obtained by dry blending 67 parts by mass of 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 min) (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 (trade name: E5100, manufactured by Toyobo Co., Ltd.) Obtained.
The conditions for 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
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC701, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 14 g / 10 min) at a resin temperature of 290 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 a T die width of 560 mm, a resin temperature of 290 ° C., and a screw rotation speed using the above-described extrusion film forming machine. Under the condition of 34 rpm, the maximum take-off speed (m / min) at which the extrusion coating film was cut or surging was measured. The measurement results were as shown in Table 1 below.

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

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

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

(5) Loop stiffness The resin films obtained in 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 a stiffness tester (manufactured by Toyo Seiki Seisakusho, trade name: Loop stiffness). 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 sealing 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 min) at a resin temperature of 320 ° C. Then, it was extruded onto a 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) to obtain a resin film. The conditions for 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 biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min) and low fossil fuel-derived Resin blended with 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 min) (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 12 μm thick PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.) A film was obtained. The conditions for 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 linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel Low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd., trade name: KC573, biomass degree: 0%, density: 0.910 g / cm ³ , MFR: 15 g / 10 minutes) and 30 parts by mass of a resin (biomass degree: 29) %, Density: 0.916 g / cm ³ , MFR: 8.4 g / 10 min) at a resin temperature of 320 ° C. and a 12 μm thick PET film (east The resin film was obtained by extruding onto a product of Yobo Co., Ltd. (trade name: E5100). The conditions for 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 linear low density polyethylene derived from biomass (manufactured by Braskem, trade name: SLL318, biomass degree: 87%, density: 0.918 g / cm ³ , MFR: 2.7 g / 10 min), fossil fuel 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 min) and 37 parts by mass, linear from fossil fuel 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) 30 parts by mass of resin (biomass degree: 29) %, Density: 0.912 g / cm ³ , MFR: 8.7 g / 10 min) at a resin temperature of 320 ° C. and a PET film having a thickness of 12 μm ( Extruded onto Toyobo Co., Ltd., trade name: E5100) to obtain a resin film. The conditions for 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
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd., trade name: LC600A, biomass degree: 0%, density: 0.919 g / cm ³ , MFR: 7 g / 10 min) at a resin temperature of 320 ° C., thickness Extruded onto a 12 μm PET film (trade name: E5100, manufactured by Toyobo Co., Ltd.), a resin film was obtained. The conditions for 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 the above Reference Examples 4 to 7 and Reference Comparative Example 2 and the properties 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 composition used in the above Reference Examples 4 to 7 and Reference Comparative Example 2 was subjected to a T die width of 560 mm, a resin temperature of 290 ° C., and a screw rotation speed by using the above extrusion film forming machine. Under the condition of 34 rpm, the maximum take-off speed (m / min) at which the extrusion coating film was cut or surging was measured. The measurement results were as shown in Table 2 below.

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

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

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

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

Example 1 (reference)
Low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene: LC701, MFR: 14, density: 0.919) and high density polyethylene derived from biomass (manufactured by Braskem: SHA7260, MFR: 20, density: 0.955, biomass Degree: 94.5%) was prepared by dry blending at 50:50. This resin was extrusion coated with a thickness of 15 μm on paper (pure white, basis weight 30 g / m ² ), and bonded to a biomass PET film (12 μm, biomass degree: 14%).

  Next, fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919) and biomass-derived as the inner core layer of the biomass PET film (12 μm, biomass degree: 14%) A high-density polyethylene (made by Braskem: SHA7260, MFR: 20, density: 0.955, biomass degree: 94.5%) was dry blended at 50:50. Further, as the sealing layer, a fossil fuel-derived linear low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: KC581, MFR: 11, density: 0.919) and a biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318). , MFR: 2.7, density: 0.918, biomass degree: 87%) and a resin obtained by melt blending at 67:33 were prepared. The above resin is coextruded at a resin temperature of 290 ° C. and 320 ° C. (core layer: 15 μm, seal layer: 5 μm) through an 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 laminate, 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 Co., Ltd .: LC701, MFR: 14, density: 0.919) is extrusion coated to a thickness of 15 μm on paper (pure white, basis weight 30 g / m ² ), and a biomass PET film ( 12 μm, biomass degree: 14%).

  Next, fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919) was prepared as the inner core layer of the biomass PET film (12 μm, biomass degree: 14%). . In addition, a fossil fuel-derived linear low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: KC581, MFR: 11, density: 0.919) was prepared as a seal layer. The above resin is coextruded at a resin temperature of 290 ° C. and 320 ° C. (core layer: 15 μm, seal layer: 5 μm) through an 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 0%. Using this laminate, a pillow bag having an outer dimension of 20 mm × 100 mm and a back seal width of 5 mm was prepared.

Each laminated body obtained in Example 1 and Comparative Example 1 was cut into a width of 15 mm and a length of 200 mm, 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 this test piece, a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.) was used to measure the peel strength at T at a tensile speed of 300 mm / min, and the temperature at which sealing was started was specified. The measurement results were as shown in Table 3 below.

Example 2
Biomass-derived PET film (thickness 12 μm, biomass degree: 14%), fossil fuel-derived low density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919 ) 50 parts by mass and biomass-derived 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, degree of biomass: 87%) is 300 ° C. via an anchor coat. Extrusion was performed at a resin temperature (15 μm), and bonded to aluminum foil (manufactured by Nippon Foil Co., Ltd .: 1N30 material, thickness 7 μm). Furthermore, on aluminum foil, 50 parts by mass of fossil fuel-derived low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919 ) and biomass-derived linear low-density polyethylene (manufactured by Braskem): A resin obtained by dry blending 50 parts by mass of SLL 318, 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). ) To obtain a laminate.

Comparative Example 2
A low-density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919 ) is applied to a biomass-derived PET film (thickness 12 μm, biomass degree: 14%) via an anchor coat. Extrusion was performed at a resin temperature of 300 ° C. (15 μm), and bonded with aluminum foil (manufactured by Nippon Foil Co., Ltd .: 1N30 material, thickness 7 μm). Furthermore, low-density polyethylene (manufactured by Nippon Polyethylene Co., Ltd .: LC701, MFR: 14, density: 0.919 ) derived from fossil fuel is applied onto the aluminum foil at a resin temperature of 300 ° C. via an anchor coat by an extrusion laminating method. Extrusion (30 μm) gave a laminate.

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

Each laminate obtained in Example 2 and Comparative Example 2 was tested except that the test conditions were a seal pressure of 30 N / cm ² , a seal time of 1 second, a seal temperature of 170 ° C., and a tensile speed of 300 mm / min. The seal strength was measured under the same conditions. The measurement results were as shown in the following table.

Example 3 (reference)
As an inner film application for a long-term storage type liquid paper container, dry lamination (manufactured by DIC: main ingredient LX-) of an aluminum foil (manufactured by Toyo Aluminum Co., Ltd., 7 μm) and a PET film derived from biomass of 12 μm thickness (manufactured by Toyobo Co., Ltd .: DE024, 12 μm) 703A / curing agent KR-90). Thereafter, the polyester film / isocyanate two-component curable anchor agent is coated on the PET film surface side, and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923)) A resin obtained by dry blending 50 parts by mass of a linear low-density polyethylene derived from biomass and 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%), 320 While extruding at a resin temperature of ° C. (20 μm, line speed 100 m / min), it was bonded to a low density polyethylene film (Dai Nippon Printing: SKL, density: 0.923, 40 μm) to obtain a laminate. The biomass degree of the entire laminate was 10%.

Comparative Example 3
As an internal film application for a long-term storage type liquid paper container, 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 product LX-703A / Bonding was performed using a curing agent KR-90). Thereafter, the polyester film / isocyanate two-component curable anchor agent is coated on the PET film surface side, and low density polyethylene derived from fossil fuel (manufactured by Nippon Polyethylene Co., Ltd .: LC520 (MFR: 3.6, density: 0.923)) A resin obtained by dry blending 50 parts by mass and 50 parts by mass of biomass-derived linear low-density polyethylene (manufactured by Braskem: SLL318, MFR: 2.7, density: 0.918, biomass degree: 87%) at 320 ° C. While extruding at a resin temperature of (20 μm, line speed 100 m / min), it was bonded to a low density polyethylene film (Dai Nippon Printing, SKL, density: 0.923, 40 μm) to obtain a laminate. The biomass degree of the entire laminate was 7%.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Biomass polyester resin layer 12 Biomass polyolefin resin layer 20 Laminated body 21 Biomass polyester resin layer 22 1st biomass polyolefin resin layer 23 2nd biomass polyolefin resin layer

Claims (13)

A biomass polyester resin layer comprising a biomass polyester resin composition comprising as a main component a polyester comprising a diol unit and a dicarboxylic acid unit, wherein the diol unit is biomass-derived ethylene glycol,
Biomass-derived polyethylene obtained by polymerizing monomers containing ethylene derived from biomass, and fossil fuel-derived polyethylene obtained by polymerizing ethylene derived from fossil fuel and ethylene derived from fossil fuel and / or α-olefin monomer. A biomass polyolefin resin layer comprising a biomass polyolefin resin composition comprising;
A barrier layer containing an inorganic substance;
A heat seal layer having a density of 0.90 to 0.925 g / cm ³ ;
Having
A laminate in which the biomass polyolefin resin layer is located between the biomass polyester resin layer and the barrier layer.   The laminate according to claim 1, wherein the biomass polyolefin resin layer comprises 5 mass% or more of the biomass-derived ethylene with respect to the entire biomass polyolefin resin layer.   The biomass polyolefin resin layer has a first biomass polyolefin resin layer and a second biomass polyolefin resin layer in order from the biomass polyester resin layer side, and the first biomass polyolefin resin layer is derived from the biomass. 5 mass% or more of ethylene is contained with respect to the whole 1st biomass polyolefin resin layer, and 2nd biomass polyolefin resin layer is 5 mass% with respect to the whole 2nd biomass polyolefin resin layer of said biomass origin ethylene. The laminate according to claim 1 or 2, comprising the above. First biomass-derived biomass polyolefin resin layer in ethylene concentration C ₁ and the second ethylene concentration C ₂ of the biomass-derived biomass polyolefin resin layer satisfies C _1> C _2, laminate of claim 3 body.   The laminated body as described in any one of Claims 1-4 in which the monomer containing ethylene derived from biomass further contains ethylene and / or alpha olefin derived from fossil fuel.   The laminate according to any one of claims 1 to 5, wherein the monomer containing ethylene derived from biomass further contains an α-olefin derived from biomass.   7. The biomass polyolefin resin composition according to claim 1, comprising 5 to 90% by mass of the biomass-derived polyethylene and 10 to 95% by mass of the fossil fuel-derived polyethylene. The laminated body of description.   The laminate according to any one of claims 1 to 7, wherein the α-olefin is butylene, hexene, or octene.   The laminate according to any one of claims 1 to 8, wherein the laminate further comprises a non-biomass polyolefin resin layer made of a resin material containing a fossil fuel-derived raw material.   The laminate according to any one of claims 1 to 9, wherein the laminate further comprises a paper layer.   It is a manufacturing method of the laminated body as described in any one of Claims 1-10, Comprising: The manufacturing method bonded together with the said barrier layer, extruding the said biomass polyolefin resin layer.   Packaged product provided with the laminated body as described in any one of Claims 1-10.   A liquid paper container comprising the laminate according to any one of claims 1 to 10.

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