JP7449502B2 - Laminated body of polyester resin composition - Google Patents

Description

The present invention relates to a laminate having a layer made of a biomass polyester resin composition obtained from plant-derived raw materials, and more specifically, a laminate comprising a resin composition containing a polyester using biomass-derived ethylene glycol as a diol component. The present invention relates to a laminate having a first layer.

Polyester has excellent mechanical properties, chemical stability, heat resistance, transparency, etc., and is inexpensive, so it is widely used in various industrial applications. Polyester is obtained by polycondensing diol units and dicarboxylic acid units. For example, polyethylene terephthalate (hereinafter sometimes abbreviated as PET) is obtained by esterifying ethylene glycol and terephthalic acid as raw materials. After that, it is produced by polycondensation reaction. These raw materials are produced from petroleum, which is a fossil resource; for example, ethylene glycol is industrially produced from ethylene, and terephthalic acid is industrially produced from xylene.

In recent years, with increasing calls for building a recycling-oriented society, there is a desire to move away from fossil fuels in the materials field as well as energy, and the use of biomass is attracting attention. Biomass is an organic compound that is photosynthesized from carbon dioxide and water, and by using it, it becomes carbon dioxide and water again, so it is a so-called carbon-neutral renewable energy. In recent years, the practical use of biomass plastics made from these biomass raw materials has progressed rapidly, and attempts are also being made to produce polyester, which is a general-purpose polymer material, from these biomass raw materials.

For example, as a polyester using a biomass raw material, a polyester consisting of isosorbide, which is one of the biomass raw materials, terephthalic acid, and ethylene glycol has been proposed (Patent Document 1).

In addition, biomass ethanol obtained by fermenting starch and sugars obtained from plants such as corn and sugarcane with microorganisms has been put into practical use, and it is possible to industrially produce ethylene glycol from this biomass ethanol via ethylene. It has also been successful.

Special Publication No. 2002-512304

The present inventors focused on ethylene glycol, which is a raw material for polyester, and found that polyester, which uses plant-derived ethylene glycol as a raw material instead of ethylene glycol obtained from conventional fossil fuels, can be obtained from conventional fossil fuels. It has been found that polyester produced using ethylene glycol is comparable in physical properties such as mechanical properties. Furthermore, we have found that laminates with layers made of biomass-derived polyester are comparable in mechanical properties and other physical properties to laminates made from conventional raw materials obtained from fossil fuels. Obtained. The present invention is based on this knowledge.

Therefore, it is an object of the present invention to provide a laminate having a layer consisting of a resin composition comprising a carbon-neutral polyester using biomass ethylene glycol, which is manufactured from raw materials obtained from conventional fossil fuels. It is an object of the present invention to provide a laminate of polyester resin films that is comparable to laminates in terms of physical properties such as mechanical properties.

The method for manufacturing a laminate according to the present invention includes :
A process of mixing and melting a biomass -derived polyester whose diol unit is biomass-derived ethylene glycol and whose dicarboxylic acid unit is fossil fuel-derived terephthalic acid, and a fossil fuel-derived polyethylene terephthalate masterbatch containing porous silica. and,
A step of mixing and melting the biomass-derived polyester and the fossil fuel-derived polyethylene terephthalate masterbatch, extruding the melt into a sheet shape, and cooling and solidifying it to obtain an unstretched sheet;
Biaxially stretching the unstretched sheet to obtain a first layer made of a biaxially stretched film;
forming a second layer on the first layer using a resin material that contains fossil fuel-derived raw materials and does not contain biomass-derived raw materials;
in this order,
The resin composition constituting the melt contains a polyester consisting of a diol unit and a dicarboxylic acid unit as a main component, and the polyester is a polyester derived from the biomass, and the diol unit is ethylene glycol derived from a fossil fuel. , a fossil fuel-derived polyester in which the dicarboxylic acid unit is fossil fuel-derived terephthalic acid, and the biomass-derived polyester is contained in an amount of 90% by mass or less based on the entire resin composition.
This is a method for manufacturing a laminate having at least two layers, the first layer and the second layer.
In an aspect of the present invention, the melting step includes the step of melting the biomass-derived polyester, the fossil fuel-derived polyethylene terephthalate masterbatch containing the porous silica, and the diol unit being a fossil fuel-derived diol or a biomass-derived ethylene glycol. This is preferably a step of mixing and melting a recycled polyester of polyester in which the dicarboxylic acid units are dicarboxylic acids derived from fossil fuels.
In an aspect of the present invention, the step of forming the second layer includes extruding and laminating a resin material containing the fossil fuel-derived raw material and not containing the biomass-derived raw material onto the first layer. It is preferable that the process be formed by a method.
In an aspect of the present invention, the step of forming the second layer includes forming a film made of a resin material containing the fossil fuel-derived raw material and not containing the biomass-derived raw material into the first layer. Preferably, this is a step of laminating on top.

According to the present invention, in a laminate having at least two layers, the first layer is made of a resin composition containing as a main component a polyester consisting of a diol unit and a dicarboxylic acid unit, and the resin composition comprises: By containing 50 to 95% by mass of a polyester whose diol unit is biomass-derived ethylene glycol and whose dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid based on the entire resin composition, a carbon-neutral resin can be obtained. A laminate having the following layers can be realized. Therefore, the amount of fossil fuel used can be significantly reduced compared to conventional methods, and the environmental load can be reduced. Furthermore, the laminate of the polyester resin composition of the present invention is a polyester resin that is comparable in physical properties such as mechanical properties to laminates of polyester resin compositions manufactured from conventional raw materials obtained from fossil fuels. Since the composition is used, it is possible to replace a conventional laminate of a polyester resin composition.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention.

<Laminated body>
In the laminate according to the present invention, the first layer is made of a resin composition containing as a main component a polyester consisting of a diol unit and a dicarboxylic acid unit, and the resin composition is such that the diol unit is ethylene glycol derived from biomass. By containing 50 to 95% by mass, preferably 50 to 90% by mass of a polyester whose dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid, based on the entire resin composition, a carbon neutral polyester resin can be obtained. It is possible to realize a laminate having layers consisting of. In addition, biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol, so polyester using biomass-derived ethylene glycol is no different from polyester polymerized from conventional fossil fuel-derived raw materials. Therefore, the first layer of the laminate of the present invention is comparable to conventional polyester films in terms of physical properties such as mechanical properties. Furthermore, since the laminate of the present invention has at least one layer made of carbon-neutral polyester resin, the amount of fossil fuel used can be reduced compared to a laminate manufactured from conventional raw materials obtained from fossil fuels. It is possible to significantly reduce the environmental impact. Further, the second layer is a resin layer made of a resin material containing a conventional fossil fuel-derived raw material. By combining the first layer and the second layer to form a laminate, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties are imparted or improved. can be done. According to a preferred embodiment, the laminate may further include a third layer made of an inorganic substance or an inorganic oxide.

According to one aspect of the present invention, a laminate having a first layer and a second layer is provided. Specifically, FIG. 1 shows a schematic cross-sectional view of an example of a laminate according to the present invention. The laminate 10 shown in FIG. 1 includes a first layer 11 on which a printed layer 13 is formed, and a second layer 12, and the printed surface 13 of the first layer 11 and the second layer 12 form a printed layer 13. The layer 12 is bonded with an adhesive layer 14 interposed therebetween.

According to one aspect of the present invention, a laminate having a first layer, a second layer, and a third layer is provided. Specifically, FIG. 2 shows a schematic cross-sectional view of an example of a laminate according to the present invention. The laminate 20 shown in FIG. 2 includes a first layer 21, a second layer 22, a third layer 23, and a second layer 25 in this order, and each layer has a They are bonded together via an adhesive layer 24.

According to one aspect of the present invention, a laminate having a first layer, a second layer, and a third layer is provided. Specifically, FIG. 3 shows a schematic cross-sectional view of an example of a laminate according to the present invention. The laminate 30 shown in FIG. 2 includes a first layer 31, a second layer 32, a third layer 33, and a second layer 34 in this order. Hereinafter, each layer structure of the present invention will be explained.

<First layer>
In the present invention, the first layer is made of a resin composition containing polyester as a main component as described below. Note that the laminate may have two or more first layers. When there are two or more first layers, they may each have the same composition or different compositions.

<Polyester>
The polyester contained in the resin composition forming the first layer consists of a diol unit and a dicarboxylic acid unit, and uses biomass-derived ethylene glycol as the diol unit and fossil fuel-derived dicarboxylic acid as the dicarboxylic acid unit. It is obtained by a polycondensation reaction.

Biomass-derived ethylene glycol is made from ethanol produced from biomass (biomass ethanol). For example, biomass-derived ethylene glycol can be obtained by converting biomass ethanol into ethylene glycol via ethylene oxide using a conventionally known method. Moreover, commercially available biomass ethylene glycol may be used, and for example, biomass ethylene glycol commercially available from India Glycol Corporation can be suitably used.

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

In addition, specific examples of aliphatic dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms. chain or alicyclic dicarboxylic acids. Further, as derivatives of aliphatic dicarboxylic acids, lower alkyl esters such as methyl esters, ethyl esters, propyl esters, and butyl esters of the above aliphatic dicarboxylic acids, and cyclic acid anhydrides of the above aliphatic dicarboxylic acids such as succinic anhydride may be used. Can be mentioned. Among these, adipic acid, succinic acid, dimer acid, or a mixture thereof is preferred, and those containing succinic acid as a main component are particularly preferred. As the aliphatic dicarboxylic acid derivative, methyl esters of adipic acid and succinic acid, or mixtures thereof are more preferred.

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

The polyester contained in the resin composition forming the first layer may be a copolymerized polyester in which a copolymerization component is added as a third component in addition to the diol component and dicarboxylic acid component described above. Specific examples of copolymerization components include bifunctional oxycarboxylic acids, trifunctional or more polyhydric alcohols, trifunctional or more polycarboxylic acids and/or their anhydrides, and trifunctional or more functional polyhydric alcohols to form a crosslinked structure. At least one type of polyfunctional compound selected from the group consisting of oxycarboxylic acids having higher than functional functions is mentioned. Among these copolymerization components, bifunctional and/or trifunctional or higher functional oxycarboxylic acids are particularly preferably used because copolymerized polyesters with a high degree of polymerization tend to be easily produced. Among these, the use of trifunctional or higher functional oxycarboxylic acids is most preferable because polyester with a high degree of polymerization can be easily produced in a very small amount without using a chain extender described later.

Moreover, the above-mentioned polyester may be a high molecular weight polyester obtained by chain extension (coupling) of these copolymerized polyesters. As a chain extender, a chain extender such as a carbonate compound or a diisocyanate compound can also be used, but the amount is usually such that carbonate bonds and urethane bonds are It is usually 10 mol% or less, preferably 5 mol% or less, more preferably 3 mol% or less.

Specifically, carbonate compounds include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, ethylene carbonate, diamyl carbonate, dicyclohexyl Examples include carbonate. In addition, carbonate compounds derived from hydroxy compounds such as phenols and alcohols and composed of the same or different hydroxy compounds 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 xylene diisocyanate. Known diisocyanates such as diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate can be mentioned.

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

The amount of diol used when producing polyester is substantially equimolar to 100 moles of dicarboxylic acid or its derivative, but generally, it is used during esterification and/or transesterification reaction and/or polycondensation reaction. Since there is distillation of

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

Examples of the polymerization catalyst generally include compounds containing metal elements from Groups 1 to 14 of the periodic table, excluding hydrogen and carbon. 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. Compounds containing organic groups, such as carboxylates, alkoxy salts, organic sulfonates, or β-diketonate salts, as well as inorganic compounds such as the metal oxides and halides mentioned above, and mixtures thereof. Among 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. Furthermore, since the polymerization rate increases when the catalyst is in a molten or dissolved state during polymerization, it is preferably a compound that is liquid during polymerization or dissolves in the ester low polymer or polyester.

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- Mention may be made of benzyl titanate and mixed titanates thereof. In addition, titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, titanium (diisoprooxide) acetylacetonate, titanium bis(ammonium lactate) dihydroxide, titanium bis(ethylacetoacetate) diisopropoxide, titanium (triethanolaminate) ) Isopropoxide, polyhydroxy titanium stearate, titanium lactate, titanium triethanolaminate, butyl titanate dimer, etc. are also suitably used. Furthermore, titanium oxide and composite oxides containing titanium and silicon are also suitably 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) are preferred, and in particular, tetra-n-butyl titanate, polyhydroxy titanium stearate , titanium (oxy)acetylacetonate, titanium tetraacetylacetonate, and titania/silica composite oxide (for example, product name: C-94 manufactured by Acordis Industrial Fibers) are preferred.

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

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

When using a metal compound as a polymerization catalyst, the lower limit of the amount of metal relative to the polyester to be produced is usually 5 ppm or more, preferably 10 ppm or more, and the upper limit is usually 30,000 ppm or less, preferably 1,000 ppm or less. More preferably it is 250 ppm or less, particularly preferably 130 ppm or less. If the amount of catalyst used is too large, it is not only economically disadvantageous but also reduces the thermal stability of the polymer, whereas if it is too small, the polymerization activity decreases and the resulting degradation of the polymer occurs during polymer production. becomes more likely to be induced. Regarding the amount of catalyst used here, a method of reducing the amount of catalyst used is a preferred embodiment because the lower the amount used, the lower the amount of terminal carboxyl groups in the polyester produced.

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. Further, the reaction time is usually about 1 hour to 10 hours.

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

High molecular weight 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 in a uniform molten state without a solvent, and reacted with the polyester obtained by polycondensation. Specifically, a polyester obtained by catalytically reacting a diol and a dicarboxylic acid, whose terminal group substantially has a hydroxyl group, and whose mass average molecular weight (Mw) is 20,000 or more, preferably 40,000 or more. By reacting the prepolymer with the chain extender, a polyester resin having a higher molecular weight can be obtained. If the prepolymer has a mass average molecular weight of 20,000 or more, it can be used even under severe conditions such as in a molten state by using a small amount of coupling agent, and will not be affected by residual catalyst, so it will not form a gel during the reaction. , high molecular weight polyesters can be produced.

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

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

Various additives may be added in the polyester manufacturing process or to the manufactured polyester as long as its properties are not impaired, such as plasticizers, ultraviolet stabilizers, color inhibitors, matting agents, etc. , a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, a mold release agent, an antioxidant, an ion exchange agent, a coloring pigment, etc. can be added. These additives are added in an amount of 5 to 50% by weight, preferably 5 to 20% by weight, based on the entire polyester resin composition.

The polyester (hereinafter also referred to as recycled polyester), which may be contained in the resin composition forming the first layer in a proportion of 5 to 45% by mass, is composed of diol units and dicarboxylic acid units, and the diol units are diol units. It is a polyester obtained by recycling a product consisting of a polyester resin obtained by a polycondensation reaction using a fossil fuel-derived diol or biomass-derived ethylene glycol as a unit and a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. .

Even if the diol unit and dicarboxylic acid unit are both made from fossil fuel-derived raw materials, the resin that is the source of recycled polyester (that is, the polyester resin before recycling) is not biomass polyester as described above. Good too.

Fossil fuel-derived diols used in the resin that is the basis of recycled polyester include aliphatic diols, aromatic diols, and derivatives thereof, and those used as diol units of conventional polyesters are preferably used. be able to. The aliphatic diol is not particularly limited as long as it is an aliphatic or alicyclic compound having two OH groups, but the lower limit of the number of carbon atoms is 2 or more, and the upper limit is usually 10 or less, preferably 6. The following aliphatic diols may be mentioned. Specific examples include ethylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, decamethylene glycol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. It will be 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 preferred, and ethylene glycol is particularly preferred.

The resin composition containing the polyester obtained as described above preferably contains 10 to 19% of biomass-derived carbon based on the total carbon in the polyester as determined by radiocarbon (C14) measurement. Since carbon dioxide in the atmosphere contains C14 at a certain rate (105.5 pMC), the C14 content in plants that grow by taking in atmospheric carbon dioxide, such as corn, is also around 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the proportion of C14 contained in all carbon atoms in polyester, the proportion of carbon derived from biomass can be calculated. In the present invention, the biomass-derived carbon content P _bio is defined as follows, where the C14 content in the polyester is P _C14 .
P _bio (%) = P _C14 /105.5×100

Taking polyethylene terephthalate as an example, polyethylene terephthalate is a polymerization of ethylene glycol containing 2 carbon atoms and terephthalic acid containing 8 carbon atoms in a molar ratio of 1:1, so only biomass-derived ethylene glycol can be used. When P bio is used, the biomass-derived carbon content P _bio in the polyester is 20%. In the present invention, the content of biomass-derived carbon as determined by radiocarbon (C14) measurement is preferably 10 to 19% based on the total carbon in the resin composition. If the biomass-derived carbon content in the resin composition is less than 10%, the effect as a carbon offset material will be poor. On the other hand, as mentioned above, the biomass-derived carbon content in the resin composition is preferably close to 20%, but due to problems in the film manufacturing process and physical properties, the resin may contain recycled polyester or Since it is preferable to include additives, the actual upper limit is 18%.

<Resin film>
The first layer of the laminate is preferably a polyester resin film made of the resin composition described above. In order to process the resin composition into a film, a conventional method for forming a film from polyester resin can be employed. Specifically, after drying the above-mentioned resin composition, it is supplied to a melt extruder heated to a temperature (Tm) above the melting point of polyester to Tm + 70°C to melt the resin composition, for example. A film can be formed by extruding the material into a sheet from a die such as a T-die, and rapidly cooling and solidifying the extruded sheet material using 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, etc. can be used depending on the purpose.

The first layer of the laminate is preferably biaxially stretched. Biaxial stretching can be performed by a conventionally known method. For example, the film extruded onto a cooling drum as described above is then heated by roll heating, infrared heating, etc., and stretched in the longitudinal direction to form a longitudinally stretched film. This stretching is preferably carried out using the difference in circumferential speed between two or more rolls. Longitudinal stretching is usually carried out at a temperature range of 50 to 100°C. Further, the longitudinal stretching ratio 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 stretching ratio is less than 2.5 times, the thickness unevenness of the polyester film becomes large and it is difficult to obtain a good film.

The longitudinally stretched film is then sequentially subjected to transverse stretching, heat setting, and heat relaxation to become a biaxially stretched film. Transverse stretching is usually carried out at 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 use. If it is less than 2.5 times, the thickness of the film becomes uneven and it is difficult to obtain a good film, and if it exceeds 5.0 times, breakage is likely to occur during film formation.

After the transverse stretching, heat setting is subsequently performed, and the preferred temperature range for heat setting is Tg+70 to Tm-10°C of the polyester. Further, the heat setting time is preferably 1 to 60 seconds. Furthermore, for applications requiring a reduction in thermal shrinkage rate, a thermal relaxation treatment may be performed as necessary.

The stretched resin film obtained as described above has an arbitrary thickness depending on its use, but is usually about 5 to 500 μm. The breaking strength of such a resin film is 5 to 40 kg/mm ² in the MD direction and 5 to 35 kg/mm ² in the TD direction, and the breaking elongation is 50 to 350% in the MD direction and 5 to 350% in the TD direction. It is 50-300%. Furthermore, the shrinkage rate when left in a temperature environment of 150° C. for 30 minutes is 0.1 to 5%. In this way, the film made of the resin composition according to the present invention has physical properties equivalent to that of a conventional polyester film made only from fossil fuel-derived materials.

<Second layer>
In the present invention, the second layer is a resin layer made of a resin material containing fossil fuel-derived raw materials. The second layer can be formed using conventionally known raw materials, and its composition and formation method are not particularly limited. When the laminate further includes a second layer, heat resistance, pressure resistance, water resistance, heat sealability, pinhole resistance, puncture resistance, and other physical properties can be imparted or improved. Note that the laminate may have two or more second layers. When there are two or more second layers, they may have the same composition or different compositions.

Examples of the second layer include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, propylene-ethylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylic acid copolymer. Resins such as polymers, ethylene-methacrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, or ionomers can be used. These resins may be formed by an extrusion lamination method, or they may be laminated as a film made in advance by a T-die method, an inflation method, etc. with a heat-resistant base material layer by a dry lamination method, an extrusion lamination method, etc. .

In addition, 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 It may also be a composite film made by laminating two or more of these films, such as a co-extruded co-stretched film / metaxylylene diamine nylon 6 or a co-extruded co-stretched polypropylene/ethylene-vinyl alcohol copolymer film.

<Third layer>
In the present invention, the third layer is made of an inorganic substance or an inorganic oxide, preferably a vapor-deposited film of an inorganic substance or an inorganic oxide, or a metal foil. The deposited film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. By further including the third layer, the laminate can provide or improve gas barrier properties that block the transmission of oxygen gas, water vapor, etc., and light shielding properties that block the transmission of visible light, ultraviolet rays, etc. Note that the laminate may have two or more third layers. When there are two or more third layers, they may each have the same composition or different compositions.

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), or other inorganic substances or evaporated films of inorganic oxides can be used. Particularly suitable for packaging materials (bags) and the like, it is preferable to use vapor-deposited films of aluminum metal, or vapor-deposited films of silicon oxide, aluminum metal, or aluminum oxide.

Inorganic oxides are expressed as, for example, MO _x such as SiO _x , _AlO expressed. The value range of X is 0 to 2 for silicon (Si), 0 to 1.5 for aluminum (Al), 0 to 1 for magnesium (Mg), 0 to 1 for calcium (Ca), Potassium (K) is 0 to 0.5, tin (Sn) is 0 to 2, sodium (Na) is 0 to 0.5, boron (B) is 0 to 1, 5, titanium (Ti) can take a value in the range of 0 to 2, lead (Pb) can take a value in the range of 0 to 1, zirconium (Zr) can take a value in the range of 0 to 2, and yttrium (Y) can take a value in the range of 0 to 1.5. In the above, when X=0, it is a completely inorganic substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material, with silicon (Si) in the range of 1.0 to 2.0 and aluminum (Al) in the range of 0.5 to 1.5. You can use the value of .

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

Examples of methods for forming the deposited film include physical vapor deposition methods (PVD methods) such as vacuum evaporation methods, sputtering methods, and ion plating methods, or plasma chemical vapor deposition methods and thermochemical methods. Examples include a chemical vapor deposition method (CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

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

<Other layers>
The laminate according to the present invention may further include at least one other layer in addition to the first to third layers. When having two or more other layers, they may have the same composition or different compositions. Other layers can be formed on any one or more of the first to third layers. Examples of other layers include a printing layer and an adhesive layer. The printing layer can be formed using conventionally known pigments and dyes, and the forming method is not particularly limited. Further, the adhesive layer is an adhesive layer or an adhesive resin layer formed to bond any two layers together by laminating. Examples of laminating adhesives include one-component or two-component curing or non-curing vinyl-based, (meth)acrylic-based, polyamide-based, polyester-based, polyether-based, polyurethane-based, epoxy-based, rubber-based, Other solvent-based, water-based, or emulsion-based laminating adhesives can be used. The coating method for the above adhesive may be, for example, a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a Fontaine method, a transfer roll coating method, or other methods. The coating amount is preferably about 0.1 g/m ² to 10 g/m ² (dry state), more preferably about 1 g/m ² to 5 g/m ² (dry state).

Further, as the adhesive resin layer, a resin layer made of a thermoplastic resin layer is used. Specifically, the adhesive resin layer materials include low-density polyethylene resin, medium-density polyethylene resin, high-density polyethylene resin, linear low-density polyethylene resin, and ethylene/α-olefin polymerized using a metallocene catalyst. 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, and ester monomer to ethylene/methyl methacrylate copolymer resin, ethylene/maleic acid copolymer resin, ionomer resin, and polyolefin resin, Alternatively, a copolymerized resin, a resin obtained by graft-modifying maleic anhydride onto a polyolefin resin, etc. can be used. These materials can be used alone or in combination.

<Layer composition>
The layer structure of the laminate of the present invention is not particularly limited as long as it has at least one first layer and at least one second layer, and may have the same layer structure as a conventional laminate film. . Also, for example, PET/PE (PEF), PET/CPP, PET/CNY, PET/PET/PE, PET/PET/CPP, PET/AL/PE, PET/AL/CPP, PET/ONY/PE, PET /ONY/CPP, ONY/PET/PE, ONY/PET/CPP, PET/PVA/PE, PET/PVA/CPP, PET/PVC/PE, PET/PVC/CPP, PET/AL/ONY/PE, PET /AL/ONY/CPP, PET/ONY/AL/PE, PET/ONY/AL/CPP, PET/Paper/PE, PET/Paper/CPP, Paper/AL/PET/PE, Paper/AL/PET/CPP , and OPP/PET/AL/OPP. It may also be laminated with a barrier film. Examples include PET/AL vapor-deposited PET/CPP, ONY/transparent vapor-deposited PET/CPP, and PET/AL vapor-deposited CPP. The names of each abbreviation are as follows. PET: polyethylene terephthalate, PE: polyethylene, PEF: polyethylene film, CNY: unstretched nylon, ONY: stretched nylon, AL: aluminum foil, CPP: unstretched polypropylene, OPP: biaxially stretched polypropylene, PVA: polyvinyl alcohol, PVC: PVC.

<Processing>
The laminate according to the present invention can be provided with surface functions such as chemical functions, electrical functions, magnetic functions, mechanical functions, friction/wear/lubrication functions, optical functions, thermal functions, and biocompatibility. It is also possible to perform secondary processing for this purpose. Examples of secondary processing include embossing, painting, adhesion, printing, metallization (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, coating, etc.). Moreover, a molded product can also be manufactured by subjecting the laminate according to the present invention to lamination processing (dry lamination or extrusion lamination), bag making processing, and other post-processing processing.

<Application>
The laminate according to the present invention can be suitably used for packaging products, various label materials, lid materials, sheet molded products, laminate tubes, etc., and is particularly suitable for use in laminated films or packaging bags (e.g., pillow bags, standing bags, etc.). pouches, 4-sided pouches, etc.) are preferred. The thickness of the laminate can be appropriately determined depending on its use. For example, it is used in the form of a film or sheet having a thickness of about 5 to 500 μm, preferably about 10 to 300 μm.

<Other aspects>
In an aspect of the present invention, the laminate has at least two layers,
The first layer is made of a resin composition containing as a main component a polyester consisting of diol units and dicarboxylic acid units, and the resin composition is such that the diol units are biomass-derived ethylene glycol and the dicarboxylic acid units are ethylene glycol derived from biomass. It contains 50 to 95% by mass of polyester, which is a dicarboxylic acid derived from fossil fuel, based on the entire resin composition,
Preferably, the second layer is made of a resin material containing fossil fuel-derived raw materials.
In an aspect of the present invention, the resin composition is a recycled resin product made of a polyester in which the diol unit is a fossil fuel-derived diol or biomass-derived ethylene glycol, and the dicarboxylic acid unit is a fossil fuel-derived dicarboxylic acid. It is preferable that the composition further contains a polyester obtained by.
In an aspect of the present invention, the resin composition preferably contains 5 to 45% by mass of the polyester obtained by recycling, based on the entire resin composition.
In an aspect of the present invention, the fossil fuel-derived dicarboxylic acid is preferably terephthalic acid.
In an aspect of the present invention, it is preferable that the resin composition further contains an additive.
In an embodiment of the present invention, it is preferable that the additive is contained in an amount of 5 to 50% by mass based on the entire resin composition.
In an aspect of the present invention, the additives include a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, and a mold release agent. , antioxidants, ion exchange agents, and colored pigments.
In an aspect of the present invention, the content of biomass-derived carbon based on radiocarbon (C14) measurement is preferably 10 to 19% based on the total carbon in the polyester.
In the aspect of the present invention, it is preferable that the first layer is a biaxially stretched resin film.
In the aspect of the present invention, it is preferable to further include a third layer made of an inorganic substance or an inorganic oxide.
In an aspect of the present invention, the laminate is preferably a laminate film or a packaging bag.

The present invention will be described below based on Examples, but the present invention is not limited thereto.

<Synthesis of biomass-derived polyester>
83 parts by mass of terephthalic acid and 62 parts by mass of biomass ethylene glycol (manufactured by India Glycol Ltd.) were supplied as a slurry to a reaction tank, and an esterification reaction was carried out at 240° C. for 5 hours by a conventional direct gravity method. Thereafter, 0.013 parts by mass of trimethyl phosphate (manufactured by Aldrich) was added (15 mmol % based on the acid component), and then the polymerization reaction was carried out under high-temperature vacuum conditions. First, the vacuum degree was raised to 4000 Pa and the polymerization temperature to 280° C. for 40 minutes, and then the vacuum degree was lowered to 200 Pa while maintaining the polymerization temperature of 280° C. to conduct a melt polymerization reaction. The reaction time was 3 hours. The synthesized polymer was discharged into running water in the form of a strand and pelletized using a pelletizer. The pellets were dried at 160° C. for 5 hours and then subjected to solid phase polymerization at 205° C. under a vacuum of 50 Pa in a nitrogen atmosphere to obtain a polymer with an intrinsic viscosity of 0.8 dl/g. Note that the intrinsic viscosity was calculated from the melt viscosity measured at 35° C. using a phenol/tetrachloroethane (component ratio: 3/2) solvent. Differential thermal analysis of the obtained polymer (equipment: Shimadzu DSC-60, measurement conditions: heating at 6°C/min in helium gas) showed a glass transition temperature of 69°C, indicating that the polymer was derived from fossil fuels. It was equivalent to known polyethylene terephthalate obtained from raw materials. Further, when the obtained biomass-derived polyethylene terephthalate was subjected to radiocarbon measurement, the content of biomass-derived carbon was 16% as determined by radiocarbon (C14) measurement.

<Film production 1>
After drying 90 parts by mass of the polyethylene terephthalate pellets obtained as described above and 10 parts by mass of a fossil fuel-derived polyethylene terephthalate masterbatch containing 200 ppm of porous silica with an average particle size of 0.9 μm as a lubricant, they were put into an extruder. The mixture was supplied, melted at 285° C., extruded into a sheet through a T-die, and cooled and solidified using a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low speed drive roll being 6.5 m/min and the speed of the high speed drive roll being 22 m/min, and further, using a tenter. A biaxially stretched polyester film 1 having a thickness of 12.02 μm was obtained by stretching in the transverse direction at a magnification of 3.5 times.

<Film production 2>
60 parts by mass of the polyethylene terephthalate pellets obtained as described above, 30 parts by mass of recycled PET (re-pelletized from lost parts in the manufacturing process such as edge loss during film formation), and the polyethylene terephthalate master used above. After drying 10 parts by mass of the batch, it was supplied to an extruder, melted at 285°C, extruded into a sheet from a T-die, and solidified by cooling with a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low speed drive roll being 6.5 m/min and the speed of the high speed drive roll being 22 m/min, and further, using a tenter. A biaxially stretched polyester film 2 having a thickness of 12.13 μm was obtained by stretching in the transverse direction at a magnification of 3.5 times.

<Film production 3>
60 parts by mass of polyethylene terephthalate (intrinsic viscosity 0.83 dl/g), which is manufactured from conventional fossil fuel-derived raw materials, and recycled PET (re-pelletized from parts lost during the manufacturing process such as edge loss during film production). After drying, 30 parts by mass and 10 parts by mass of the polyethylene terephthalate masterbatch used above were supplied to an extruder, melted at 285°C, extruded into a sheet form from a T-die, cooled with a cooling roll, and solidified to form an unfinished product. A stretched sheet was obtained. Next, this unstretched sheet was stretched in the longitudinal direction at a magnification of 3.5 times with the speed of the low speed drive roll being 6.5 m/min and the speed of the high speed drive roll being 22 m/min, and further, using a tenter. A biaxially stretched polyester film 3 having a thickness of 12.06 μm was obtained by stretching in the transverse direction at a magnification of 3.5 times.

<Radiation carbon measurement>
When the obtained film 1 was subjected to radiation carbon measurement, the content of biomass-derived carbon was 14% as determined by radiocarbon (C14) measurement. Furthermore, when films 2 and 3 were similarly subjected to radiation carbon measurement, the biomass-derived carbon content was 10% and 0%, respectively.

<Film evaluation>
Each of the obtained films was cut into a test piece with a width of 15 mm and a length of 200 mm from each of the MD direction (winding direction) and TD direction (direction made at a 90 degree angle with the MD direction). The strength and elongation of the test piece was measured using RTC-125A (manufactured by Orientech Co., Ltd.) in an environment of a temperature of 23° C. and a humidity of 50 RH%. Further, the F5 value (tensile strength when the film is stretched by 5%) in the MD direction and the TD direction was measured. The tensile strength (kg/mm ² ) and elongation at break (%) in the MD direction and TD direction, as well as the F5 value (kg/mm ² ), were as shown in Table 1.

In addition, test pieces cut out from each of the MD and TD directions were placed in a heating oven at 150°C and heat treated at 150°C for 30 minutes in accordance with JIS/C-2318, and the heat shrinkage rate was measured. The results were as shown in Table 1.

In addition, each film obtained above was cut into a test piece with a width of 50 mm and a length of 50 mm, and this test piece was measured using a haze meter (NDH4000, manufactured by Nippon Denshoku Kogyo Co., Ltd.) at 23 ° C. and a humidity of 50 RH%. The haze of the film was measured under the following conditions. The measurements were performed in accordance with JIS K7136:2000. The measurement results were as shown in Table 1 below.

In addition, a mixed solution for wet tension test (manufactured by Wako Pure Chemical Industries, Ltd.) was used on test pieces cut out to 50 mm in width and 50 mm in length for both those with and without corona treatment on the surface of each film. The wetting tension was measured under an environment of 23°C and humidity of 50RH%. The measurements were conducted in accordance with JIS K6768:1999. The measurement results were as shown in Table 1 below.

In addition, the friction coefficient between the test pieces whose surfaces obtained above were subjected to corona treatment and the friction coefficient between test pieces whose surfaces were not subjected to corona treatment were measured using a friction coefficient measuring device (AFT-200, Daiei Kagaku Seiki Seisakusho Co., Ltd.). The measurement was carried out using a 23° C. and 50 RH% humidity environment. The measurements were conducted in accordance with JIS K7125:1999. The measurement results were as shown in Table 1 below.

In addition, as a comparison control, a general polyester film 4 (E-5100, manufactured by Toyobo Co., Ltd.) was prepared. Catalog values for the physical properties of Film 4 are also listed in Table 1.

As is clear from Table 1, polyethylene terephthalate films (biomass PET films) 1 and 2 synthesized using biomass-derived ethylene glycol are different from polyester films (PET films) produced from raw materials obtained from conventional fossil fuels. ) It can be seen that it has physical properties comparable to those of 3 and 4.

Example 1
<Preparation of laminate 1>
One side of the biomass PET film 1 (thickness: 12 μm) obtained as described above was subjected to corona treatment. Then, a printed layer (design and white press) was formed on the corona-treated surface of the biomass PET film 1. Next, the printed surface of the biomass PET film 1 and a general linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd.: T.U.X FC-D, thickness 80 μm) were laminated by dry lamination. , a laminated film was obtained. The printing ink used was NEW LP Super manufactured by Toyo Ink. For dry lamination, use a urethane adhesive (Mitsui Chemicals: Takelac A-515V/Takenate A-5) and apply it to a gravure plate so that the dry coating amount is 3.5 g/ ^m2 . It was applied. After lamination, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch with outer dimensions of 100 mm x 140 mm, a folding width of 30 mm, and a seal width of the outer periphery of 5 mm was created.

Example 2
<Preparation of laminate 2>
Biomass PET film 1 (thickness 12 μm) obtained as described above, general nylon film (manufactured by Toyobo Co., Ltd.: Harden N1200, thickness 15 μm), aluminum foil (manufactured by Nihon Seifaku Co., Ltd.: 1N30 material, 7 μm thick) and an unstretched polypropylene film (manufactured by Futamura Chemical Co., Ltd.: FRTK-G, thickness 70 μm) were dry laminated in this order to obtain a laminated film. For dry lamination, use a urethane adhesive (Mitsui Chemicals: Takelac A-515V/Takenate A-5) and apply it to a gravure plate so that the dry coating amount is 3.5 g/ ^m2 . It was applied. After lamination, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a four-sided pouch with outer dimensions of 130 mm x 170 mm and a seal width of 10 mm at the outer periphery was created.

Example 3
<Preparation of laminate 3>
The biomass PET film 1 (thickness: 12 μm) obtained as described above and aluminum foil (manufactured by Nihon Seifaku Co., Ltd.: 1N30 material, thickness: 7 μm) were extruded and laminated at 300°C to produce low-density polyethylene ( It was laminated with Z568 (manufactured by Ube Maruzen Polyethylene Co., Ltd., thickness 15 μm). Also on the aluminum foil, low density polyethylene (manufactured by Ube Maruzen Polyethylene Co., Ltd.: Z568, thickness 30 μm) was extruded through an anchor coating agent at a resin temperature of 300° C. to obtain a laminated film. This laminated film had a layer structure as shown in FIG. Using this laminated film, a pillow bag with external dimensions of 100 mm x 150 mm and a back seal width of 10 mm was created.

Comparative example 1
<Preparation of laminate 4>
One side of the general PET film 4 (thickness: 12 μm) prepared above was subjected to corona treatment. Then, a printed layer (design and white press) was formed on the corona-treated surface of the PET film 4. Next, the printed surface of the PET film 4 and a general linear low-density polyethylene film (manufactured by Mitsui Chemicals Tohcello Co., Ltd.: T.U.X FC-D, thickness 80 μm) were laminated together by dry lamination. A laminated film was obtained. The printing ink used was NEW LP Super manufactured by Toyo Ink. For dry lamination, use a urethane adhesive (Mitsui Chemicals: Takelac A-515V/Takenate A-5) and apply it to a gravure plate so that the dry coating amount is 3.5 g/ ^m2 . It was applied. After lamination, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a standing pouch with outer dimensions of 100 mm x 140 mm, a folding width of 30 mm, and a seal width of the outer periphery of 5 mm was created.

Comparative example 2
<Preparation of laminate 5>
General PET film 4 (thickness 12 μm) prepared above, general nylon film (manufactured by Toyobo Co., Ltd.: Harden N1200, thickness 15 μm), and aluminum foil (manufactured by Nihon Seifaku Co., Ltd.: 1N30 material, thickness 7 μm) ) and an unstretched polypropylene film (manufactured by Futamura Chemical Co., Ltd.: FRTK-G, thickness 70 μm) were dry laminated in this order to obtain a laminated film. For dry lamination, use a urethane adhesive (Mitsui Chemicals: Takelac A-515V/Takenate A-5) and apply it to a gravure plate so that the dry coating amount is 3.5 g/ ^m2 . It was applied. After lamination, aging was performed at 40° C. for 48 hours. This laminated film had a layer structure as shown in FIG. Using this laminated film, a four-sided pouch with outer dimensions of 130 mm x 170 mm and a seal width of 10 mm at the outer periphery was created.

Comparative example 3
<Preparation of laminate 6>
Low-density polyethylene (Ube Maruzen polyethylene) is made by extruding the general PET film 4 (thickness 12 μm) prepared above and aluminum foil (manufactured by Nihon Faku Co., Ltd.: 1N30 material, thickness 7 μm) at 300°C by extrusion lamination method. (manufactured by Z568, thickness 15 μm). Also on the aluminum foil, low density polyethylene (manufactured by Ube Maruzen Polyethylene Co., Ltd.: Z568, thickness 30 μm) was extruded through an anchor coating agent at a resin temperature of 300° C. to obtain a laminated film. This laminated film had a layer structure as shown in FIG. Using this laminated film, a pillow bag with external dimensions of 100 mm x 150 mm and a back seal width of 10 mm was created.

<Evaluation of laminate>
Each laminated film obtained in Example 1 and Comparative Example 1 was cut into a piece with a width of 15 mm and a length of 200 mm to prepare a test piece. The PET film and the polyethylene film were peeled off, and the T-time peel strength was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientech Co., Ltd.). The tensile speed in this measurement was 50 mm/min. The measurement results were as shown in Table 2 below.

Each laminated film obtained in Example 1 and Comparative Example 1 was cut into a piece with a width of 15 mm and a length of 200 mm to prepare a test piece. The seal layer surfaces of the test pieces were bonded together by heat sealing. The T-time peel strength of the bonded sample was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientech Co., Ltd.). In this measurement, the sealing pressure was 30 N/cm ² , the sealing time was 1 second, the sealing temperature was 180° C., and the tensile speed was 300 mm/min. The measurements were conducted in accordance with JIS Z1707. The measurement results were as shown in Table 2 below.

Each of the standing pouches obtained in Example 1 and Comparative Example 1 was filled with 80 cc of water, and the unsealed part (upper edge) was sealed to produce a water-filled standing pouch. A drop impact test was conducted by dropping the produced standing pouch containing water from a height of 50 cm. The measurement results were as shown in Table 2 below.

Each of the laminated films obtained in Example 2 and Comparative Example 2 was cut into a piece with a width of 15 mm and a length of 200 mm to prepare a test piece. The PET film and the nylon film were peeled off, and the T-time peel strength was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientech Co., Ltd.). The tensile speed in this measurement was 50 mm/min. In addition, the nylon film and aluminum foil and the aluminum foil and unstretched polypropylene film were each peeled off, and the T-time peel strength was measured under the same conditions. All measurement results were as shown in Table 3 below.

Each laminated film obtained in Example 2 and Comparative Example 2 was tested under the same conditions as above except that the sealing pressure was 30 N/cm ² , the sealing time was 1 second, the sealing temperature was 200°C, and the tensile speed was 300 mm/min. The seal strength was measured under the same conditions. The measurement results were as shown in Table 3 below.

In Example 2 and Comparative Example 2, after filling with 180 cc of water, the outer periphery was sealed to produce a four-sided water-filled pouch. The produced four-sided pouch containing water was subjected to heat and pressure sterilization (Hisaka Seisakusho Co., Ltd.: RCS-60/10RSPXT) at 120° C. for 30 minutes, and a retort resistance test was conducted. The measurement results were as shown in Table 3 below.

The four-way pouch containing water prepared above was subjected to a compression resistance test by applying a static pressure of 40 kg for 3 minutes. The measurement results were as shown in Table 3 below.

Openability was confirmed by tearing the sealed portion of the water-filled four-sided pouch prepared above. The results were as shown in Table 3 below.

Each of the laminated films obtained in Example 3 and Comparative Example 3 was cut into a piece with a width of 15 mm and a length of 200 mm to prepare a test piece. The PET film and the aluminum foil were peeled off, and the T-time peel strength was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientech Co., Ltd.). The tensile speed in this measurement was 50 mm/min. The measurement results were as shown in Table 4 below.

The laminated films obtained in Example 3 and Comparative Example 3 were tested under the same conditions as above except that the sealing pressure was 30 N/cm ² , the sealing time was 1 second, the sealing temperature was 170°C, and the tensile speed was 300 mm/min. The seal strength was measured under the same conditions. The measurement results were as shown in Table 4 below.

As is clear from Tables 2 to 4, the laminate having a layer made of polyethylene terephthalate film synthesized using biomass-derived ethylene glycol is superior to the laminate having a layer made of existing polyester film. It can be seen that it has comparable physical properties.

10 laminate 11 first layer 12 second layer 13 printed layer 14 adhesive layer 20 laminate 21 first layer 22 second layer 23 third layer 24 adhesive layer 25 second layer 30 laminate 31 th 1st layer 32 2nd layer 33 3rd layer 34 2nd layer

Claims (4)

A process of mixing and melting a biomass -derived polyester whose diol unit is biomass-derived ethylene glycol and whose dicarboxylic acid unit is fossil fuel-derived terephthalic acid, and a fossil fuel-derived polyethylene terephthalate masterbatch containing porous silica. and,
A step of mixing and melting the biomass-derived polyester and the fossil fuel-derived polyethylene terephthalate masterbatch, extruding the melt into a sheet shape, and cooling and solidifying it to obtain an unstretched sheet;
Biaxially stretching the unstretched sheet to obtain a first layer made of a biaxially stretched film;
forming a second layer on the first layer using a resin material that contains fossil fuel-derived raw materials and does not contain biomass-derived raw materials;
in this order,
The resin composition constituting the melt contains a polyester consisting of a diol unit and a dicarboxylic acid unit as a main component, and the polyester is a polyester derived from the biomass, and the diol unit is ethylene glycol derived from a fossil fuel. , a fossil fuel-derived polyester in which the dicarboxylic acid unit is fossil fuel-derived terephthalic acid, and the biomass-derived polyester is contained in an amount of 90% by mass or less based on the entire resin composition.
A method for manufacturing a laminate having at least two layers, the first layer and the second layer. The melting step includes the biomass-derived polyester, the fossil fuel-derived polyethylene terephthalate masterbatch containing the porous silica, the diol unit being a fossil fuel-derived diol or biomass-derived ethylene glycol, and the dicarboxylic acid unit 2. The method for manufacturing a laminate according to claim 1, wherein the polyester is a fossil fuel-derived dicarboxylic acid and the recycled polyester is mixed and melted. The step of forming the second layer is a step of forming a resin material containing the fossil fuel-derived raw material and not containing the biomass-derived raw material on the first layer by an extrusion lamination method. , A method for manufacturing a laminate according to claim 1 or 2. The step of forming the second layer is a step of laminating a film made of a resin material containing the fossil fuel-derived raw material and not containing the biomass-derived raw material on the first layer. , A method for manufacturing a laminate according to claim 1 or 2.