JP6260597B2 - Laminate 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 a plant-derived raw material, and more specifically, 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.

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

  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 biomass as raw materials have been rapidly put into practical use, and attempts have been made to produce polyester, which is a general-purpose polymer material, from these biomass raw materials.

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

  Biomass ethanol obtained by fermenting starch and saccharides obtained from plants such as corn and sugarcane with microorganisms has been put into practical use, and ethylene glycol is industrially produced from this biomass ethanol via ethylene. Has also succeeded.

Special table 2002-512304 gazette

The present inventors pay attention to ethylene glycol, which is a raw material of polyester, and instead of ethylene glycol obtained from conventional fossil fuel, polyester using plant-derived ethylene glycol as its raw material is obtained from conventional fossil fuel. The inventors obtained knowledge that polyesters produced using ethylene glycol and those inferior in physical properties such as mechanical properties can be obtained.
Furthermore, a laminate having a layer made of such a biomass-derived polyester can also be obtained from a laminate made of a raw material obtained from a conventional fossil fuel, and a material inferior in terms of physical properties such as mechanical properties. Obtained. The present invention is based on this finding.

  Accordingly, an object of the present invention is to provide a laminate having a layer made of a resin composition containing carbon neutral polyester using biomass ethylene glycol, which is manufactured from a raw material obtained from a conventional fossil fuel. The object is to provide a laminate of a polyester resin film that is inferior in terms of physical properties such as laminate and mechanical properties.

The laminate according to the present invention has at least two layers,
The first layer is composed of a resin composition comprising as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, and the resin composition is ethylene glycol derived from biomass and having a dicarboxylic acid unit. The polyester which is a dicarboxylic acid derived from fossil fuel comprises 50 to 95% by mass with respect to the entire resin composition,
The second layer is made of a resin material containing a biomass-derived raw material.

  In an embodiment of the present invention, the resin composition is a recycled resin product comprising a polyester in which the diol unit is a diol derived from fossil fuel or ethylene glycol derived from biomass, and the dicarboxylic acid unit is a dicarboxylic acid derived from fossil fuel. It is preferable that the polyester further obtained is obtained.

  In the aspect of this invention, it is preferable that the said resin composition contains 5-45 mass% of polyester obtained by the said recycling with respect to the whole resin composition.

  In the embodiment of the present invention, the dicarboxylic acid derived from the fossil fuel is preferably terephthalic acid.

  In the embodiment of the present invention, it is preferable that the resin composition further comprises an additive.

  In the aspect of this invention, it is preferable to contain the said additive 5-50 mass% with respect to the whole resin composition.

  In an embodiment of the present invention, the additive is a plasticizer, an ultraviolet stabilizer, a coloring inhibitor, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a yarn friction reducing agent, and a release agent. It is preferable that it is 1 type, or 2 or more selected from the group which consists of an antioxidant, an ion exchanger, and a coloring pigment.

  In the aspect of this invention, it is preferable that content of the carbon derived from biomass by a radioactive carbon (C14) measurement is 10-19% with respect to all the carbon in the said polyester.

  In the embodiment of the present invention, it is preferable that the first layer is a resin film formed by biaxial stretching.

  In an embodiment of the present invention, the second layer is derived from one or more biomass selected from the group consisting of cellophane, starch, polylactic acid, polyethylene, polypropylene, nylon, polymethylene terephthalate, polyethylene terephthalate, and cellulose. The resin material is preferably used.

  In the embodiment of the present invention, it is preferable to further have a third layer made of an inorganic substance or an inorganic oxide.

  In the embodiment of the present invention, the laminate is preferably a laminated film or a packaging bag.

According to the present invention, in the laminate having at least two layers, the first layer is composed of a resin composition comprising as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, and the resin composition comprises: 50 to 95% by mass of a polyester in which the diol unit is ethylene glycol derived from biomass and the dicarboxylic acid unit is dicarboxylic acid derived from fossil fuel, based on the entire resin composition, and the second layer is derived from biomass By using the resin material containing the raw material, a laminate having a layer made of carbon neutral resin 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 of the polyester resin composition of the present invention is a polyester resin that is inferior in terms of physical properties such as mechanical properties as compared with a laminate of a polyester resin composition produced from a raw material obtained from a conventional fossil fuel. Since the composition is used, the laminate of the conventional polyester resin composition can be substituted.

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.

<Laminated body>
In the laminate according to the present invention, the first layer is composed of a resin composition comprising as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, and the resin composition comprises ethylene glycol whose diol unit is derived from biomass. And a carbon neutral polyester resin comprising 50 to 95% by weight, preferably 50 to 90% by weight, of the polyester whose dicarboxylic acid unit is a dicarboxylic acid derived from fossil fuel, based on the whole resin composition. A laminate having a layer made of can be realized. Biomass-derived ethylene glycol has the same chemical structure as conventional fossil fuel-derived ethylene glycol. Therefore, polyester using biomass-derived ethylene glycol is not a polyester polymerized from a conventional fossil fuel-derived raw material. Therefore, the first layer of the laminate of the present invention is not inferior to the conventional polyester film in terms of physical properties such as mechanical properties. Moreover, since the 2nd layer of the laminated body of this invention consists of a resin material containing the raw material derived from biomass, a 2nd layer is also a layer which consists of a carbon neutral material. Therefore, since the laminate of the present invention has at least two layers made of carbon neutral material, the amount of fossil fuel used is greatly reduced compared to a laminate manufactured from a raw material obtained from a conventional fossil fuel. Can reduce the environmental load. Moreover, according to a preferable aspect, the laminate may further include a third layer made of an inorganic substance or an inorganic oxide, or a fourth layer made of a raw material obtained from a conventional fossil fuel.

  According to one embodiment of the present invention, a stacked body including a first layer and a second layer is provided. Specifically, a schematic cross-sectional view of an example of a laminate according to the present invention is shown in FIG. A stacked body 10 shown in FIG. 1 includes a first layer 11 and a second layer 12 stacked on one surface of the first layer 11.

  According to one embodiment of the present invention, a stacked body including 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. A stacked body 20 shown in FIG. 2 includes a first layer 21, a third layer 23 deposited on one surface of the first layer 21, and a second layer 22 on which a printing layer 25 is formed. The printed surface of the second layer 22 and the third layer 23 are bonded via an adhesive layer 24. Further, the fourth layer is bonded to the other surface of the first layer 21 via the adhesive layer 24. Hereinafter, each layer structure of this invention is demonstrated.

<First layer>
In the present invention, the first layer is made of a resin composition containing a polyester described below as a main component. Note that the stacked body may include two or more first layers. In the case of having two or more first layers, each may have the same composition or a different composition.

<Polyester>
The polyester contained in the resin composition forming the first layer is composed of a diol unit and a dicarboxylic acid unit, using ethylene glycol derived from biomass as the diol unit, and using dicarboxylic acid derived from fossil fuel as the dicarboxylic acid unit. Obtained by a polycondensation reaction.

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

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

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

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

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

  The polyester may be a high molecular weight polyester obtained by chain extending (coupling) these copolyesters. As the chain extender, a chain extender such as a carbonate compound or a diisocyanate compound can also be used. However, the amount of the chain extender is usually 100% by mole of all monomer units constituting the polyester, and a carbonate bond and a urethane bond. Usually, it is 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.

  The polyester forming the first layer 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 in producing the polyester is substantially equimolar with respect to 100 mol of the dicarboxylic acid or derivative thereof, but in general, during the esterification and / or transesterification reaction and / or the condensation polymerization reaction. Is used in excess of 0.1 to 20 mol%.

  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 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 these polymerization catalysts, 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 relative to the produced polyester. More preferably, it is 250 ppm or less, Especially preferably, it is 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. The amount of catalyst used here is a preferred embodiment because the amount of terminal carboxyl groups of the polyester produced is reduced as the amount used is reduced.

  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 completion of polycondensation, the chain extender is added to the reaction system without solvent in a uniform molten state and 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 without solvent in a uniform molten state and reacted with the polyester obtained by polycondensation. Specifically, a polyester obtained by catalyzing a diol and a dicarboxylic acid and having a terminal group substantially having a hydroxyl group and a weight average molecular weight (Mw) of 20,000 or more, preferably 40,000 or more. By reacting the chain extender with the prepolymer, 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, 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. High molecular weight polyester can be produced.

  The obtained polyester may be solidified after solidification as necessary in order to further increase the degree of polymerization and to remove oligomers such as cyclic trimers. Specifically, after the polyester is made into chips 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 inactive at a temperature of 190 to 230 ° C. It is carried out by heating for 1 to several tens of hours under gas flow or under reduced pressure.

  The intrinsic viscosity (measured at 35 ° C. with an orthochlorophenol solution) of the polyester obtained as described above is preferably 0.5 dl / g to 1.5 dl / g, more preferably 0.6 dl / g. g to 1.2 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, mechanical properties required for a 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 manufactured polyester or within the range in which the properties are not impaired, for example, plasticizers, UV stabilizers, anti-coloring agents, and matting agents. Deodorizers, 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 entire polyester resin composition.

  The polyester that may be contained in the resin composition forming the first layer in a proportion of 5 to 45% by mass (hereinafter also referred to as recycled polyester) is composed of a diol unit and a dicarboxylic acid unit. 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 dicarboxylic acid unit and using a fossil fuel-derived dicarboxylic acid as a dicarboxylic acid unit. .

  Resin that is the basis of recycled polyester (that is, polyester resin before recycling) is a biomass polyester as described above, even if both diol units and dicarboxylic acid units are made of raw materials derived from fossil fuels. Also good.

  Examples of the diol derived from fossil fuel used for the resin used as the base of the 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 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.

It is preferable that the resin composition containing the polyester obtained as described above contains 10 to 19% of the biomass-derived carbon content based on the measurement of radioactive carbon (C14) with respect to the total carbon in the polyester. 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 the carbon atoms in the polyester. In the present invention, in the case where the content of C14 in the polyester and P _C14, the content of P _{bio Bio} carbon from biomass, are 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 polyester is 20%. In this invention, it is preferable that content of carbon derived from biomass by radioactive carbon (C14) measurement is 10 to 19% with respect to the total carbon in the resin composition. When the carbon content derived from biomass in the 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 resin composition is preferably closer to 20%, but from the viewpoint of problems and physical properties in the production process of the film, the recycled polyester or Since it is preferable to include an additive, the actual upper limit is 18%.

<Resin film>
It is preferable that the 1st layer of a laminated body is a polyester resin film which consists of an above-described resin composition. In order to process the resin composition into a film, a conventional method of forming a film from a polyester resin can be employed. Specifically, after drying the resin composition described above, the resin composition is supplied to a melt extruder heated to a temperature equal to or higher than the melting point of the polyester (Tm) to Tm + 70 ° C. to melt the resin composition, for example, A film can be formed by extruding into a sheet form from a die such as a T die, and rapidly solidifying the extruded sheet with a rotating cooling drum or the like. As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

  The 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 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 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.

  A heat setting treatment is subsequently performed after the transverse stretching, and a preferable temperature range for heat setting is Tg + 70 to Tm-10 ° C. of 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 film which consists of a resin composition by this invention is equivalent to the physical property of the polyester film manufactured only from the material derived from the conventional fossil fuel.

<Second layer>
In the present invention, the second layer is made of a resin material containing a biomass-derived raw material. By forming the second layer from a resin material containing a biomass-derived raw material, a carbon neutral resin layer can be formed. Therefore, the amount of fossil fuel used can be greatly reduced, and the environmental load can be reduced. Note that the stacked body may include two or more second layers. When two or more second layers are provided, each may have the same composition or a different composition.

  The second layer may be made of one or more biomass-derived resin materials selected from the group consisting of cellophane, starch, polylactic acid, polyethylene, polypropylene, nylon, polymethylene terephthalate, polyethylene terephthalate, and cellulose. preferable. The biomass material should just be used for the resin material which forms a 2nd layer for at least one part. The second layer can be formed by a conventionally known method and is not particularly limited. In the present invention, the first layer and the second layer may be formed from the same raw material derived from biomass (for example, biomass ethanol). Furthermore, you may synthesize | combine the resin material for forming a 2nd layer using commercially available biomass ethylene glycol similarly to a 1st layer. The composition of the second layer may be the same composition as the composition of the first layer.

  In addition, the resin film single-piece | unit (for example, biomass-derived polylactic acid film) manufactured from the biomass-derived raw material which existed conventionally had the necessity for the further improvement in physical properties, such as heat resistance and intensity | strength. In the laminate of the present invention, a layer made of a carbon neutral resin is used by combining the first layer made of the above-mentioned polyester resin composition and the second layer made of a conventional biomass-derived resin. A laminate having two or more can be produced. As the second layer, a commercially available polylactic acid film may be used. For example, a polylactic acid film commercially available from Mitsui Chemical Tosero Co., Ltd. can be suitably used.

<Third layer>
In the present invention, the third layer is made of an inorganic material or an inorganic oxide, and is preferably made of a vapor deposited film of an inorganic material 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 third 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 stacked body may include two or more third layers. When two or more third 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 third 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.

<Fourth layer>
In this invention, a 4th layer is a resin layer obtained from the raw material derived from the conventional fossil fuel.
The fourth layer can be formed using a conventionally known raw material, and its composition and formation method are not particularly limited. When the laminate further includes the fourth 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 stacked body may include two or more fourth layers. When two or more fourth layers are provided, each may have the same composition or a different composition.

  Examples of the fourth 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, and ionomers 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.

<Other layers>
The laminate according to the present invention may further include at least one other layer in addition to the first to fourth layers. 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 first to fourth 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.

<Layer structure>
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 second layer, respectively, and may have the same layer structure as a conventional laminated film. . 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 etc. are mentioned. Moreover, you may laminate | stack with a barrier film. For example, PET / AL vapor deposition PET / CPP, ONY / transparent vapor deposition PET / CPP, PET / AL vapor deposition CPP, etc. are mentioned. In addition, the name of each abbreviation is 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 is provided with chemical functions, electrical functions, magnetic functions, mechanical functions, friction / abrasion / lubrication functions, optical functions, thermal functions, surface functions such as biocompatibility, etc. For the purpose, it is also possible to perform secondary processing. Examples of secondary processing include embossing, painting, adhesion, printing, metalizing (plating, etc.), machining, surface treatment (antistatic treatment, corona discharge treatment, plasma treatment, photochromism treatment, physical vapor deposition, chemical vapor deposition, Coating, etc.). Further, the laminate according to the present invention can be subjected to laminating processing (dry laminating or extrusion laminating), bag making processing, and other post-processing processing to produce a molded product.

<Application>
The laminate according to the present invention can be suitably used for packaging products, various label materials, lid materials, sheet molded products, laminated tubes and the like, and in particular, laminated films or packaging bags (for example, pillow bags, standings). Pouches such as pouches and 4-way pouches) are preferred. The thickness of the laminate can be appropriately determined according to the application. 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.

  Hereinafter, although the present invention is explained based on an example, the present invention is not limited to these.

Example 1
<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) were supplied as a slurry to the reaction vessel, and the esterification reaction was carried out at 240 ° C. for 5 hours by a conventional direct weight method. Thereafter, 0.013 parts by mass of trimethyl phosphate (manufactured by Aldrich) was added (15 mmol% with respect to the acid component), and then the polymerization reaction was performed under a high-temperature vacuum condition. First, in 40 minutes, the degree of vacuum was raised to 4000 Pa and the polymerization temperature was 280 ° C., and then the degree of vacuum was lowered to 200 Pa while maintaining the polymerization temperature at 280 ° C. to carry out a melt polymerization reaction. The reaction time was 3 hours. The synthesized polymer was discharged into running water in the form of strands and pelletized by 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 having an intrinsic viscosity of 0.8 dl / g. The intrinsic viscosity was calculated from the melt viscosity measured at 35 ° C. using a phenol / tetrachloroethane (component ratio: 3/2) solvent. When the obtained polymer was subjected to differential thermal analysis (apparatus: Shimadzu DSC-60, measurement condition: helium gas, heated at 6 ° C./min), the glass transition temperature was 69 ° C., which was derived from fossil fuel. It was equivalent to the known polyethylene terephthalate obtained from the raw material. Moreover, when the carbon-made measurement of the obtained biomass-derived polyethylene terephthalate was performed, the content of biomass-derived carbon as measured by radioactive carbon (C14) was 16%.

<Production of film 1>
After drying 90 parts by mass of the polyethylene terephthalate pellets obtained as described above and 10 parts by mass of a polyethylene terephthalate masterbatch derived from a fossil fuel containing 200 ppm of porous silica having an average particle size of 0.9 μm as a lubricant, it is fed into an extruder. It was fed, melted at 285 ° C., extruded into a sheet form from a T die, and cooled and solidified with a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched at a magnification of 3.5 times in the longitudinal direction at a speed of the low speed drive roll of 6.5 m / min and a speed of the high speed drive roll of 22 m / min. 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.

<Production 2 of film>
60 parts by mass of the polyethylene terephthalate pellets obtained as described above, 30 parts by mass of recycled PET (re-pelleted in-process loss parts such as ear 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 form from a T die, and cooled and solidified with a cooling roll to obtain an unstretched sheet. Next, this unstretched sheet was stretched at a magnification of 3.5 times in the longitudinal direction at a speed of the low speed drive roll of 6.5 m / min and a speed of the high speed drive roll of 22 m / min. 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.

<Production 3 of film>
60 parts by mass of polyethylene terephthalate (inherent viscosity: 0.83 dl / g) manufactured from raw materials derived from conventional fossil fuels, and recycled PET (re-pelletized loss parts in the manufacturing process such as ear loss during film formation) 30 parts by mass and 10 parts by mass of the polyethylene terephthalate masterbatch used above are dried and then supplied to an extruder, melted at 285 ° C., extruded into a sheet form from a T-die, and cooled and solidified by a cooling roll. A stretched sheet was obtained.
Next, this unstretched sheet was stretched at a magnification of 3.5 times in the longitudinal direction at a speed of the low speed drive roll of 6.5 m / min and a speed of the high speed drive roll of 22 m / min. 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 as measured by radioactive carbon (C14) was 14%. Moreover, when the radiation carbon measurement was similarly performed about the films 2 and 3, the content of carbon derived from biomass was 10% and 0%, respectively.

<Evaluation of film>
From each of the obtained film in the MD direction (winding direction) and the TD direction (direction made by an angle of 90 degrees with the MD direction), a test piece was cut into a width of 15 mm and a length of 200 mm, and a tensile tester (Tensilon). Using RTC-125A (Orientec Co., Ltd.), the tensile strength of the test piece was measured in an environment of a temperature of 23 ° C. and a humidity of 50 RH%. In addition, F5 values in MD and TD directions (tensile strength when the film was stretched 5%) were measured. Table 1 shows the tensile strength (kg / mm ² ) and elongation at break (%), and F5 value (kg / mm ² ) in the MD direction and TD direction, respectively.

  Moreover, the test piece cut out from each of MD direction and TD direction was put into a 150 degreeC heating oven, and the heat shrink rate when heat-treating for 30 minutes at 150 degreeC based on JIS / C-2318 was measured. The results were as shown in Table 1.

  In addition, each film obtained above was cut into a width of 50 mm and a length of 50 mm to obtain a test piece. Using this test piece, a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.) was used at 23 ° C. and humidity of 50 RH%. The haze measurement of the film was performed under the environment. The measurement was performed according to JIS K7136: 2000. The measurement results were as shown in Table 1 below.

  In addition, for each of the film surfaces subjected to corona treatment and those not subjected to the corona treatment, a wet tension test mixed solution (manufactured by Wako Pure Chemical Industries, Ltd.) is used for a test piece cut to a width of 50 mm and a length of 50 mm. Then, the wetting tension was measured in an environment of 23 ° C. and humidity of 50 RH%. The measurement was performed according to JIS K6768: 1999. The measurement results were as shown in Table 1 below.

  Further, the friction coefficient between the test pieces subjected to the corona treatment on the surface obtained above and the friction coefficient between the test pieces not subjected to the corona treatment were measured using a friction coefficient measuring device (AFT-200, Daiei Scientific Instruments Co., Ltd.). The measurement was performed in an environment of 23 ° C. and humidity of 50 RH%. The measurement was performed according to JIS K7125: 1999. The measurement results were as shown in Table 1 below.

  Further, as a comparative control, a general polyester film 4 (E-5100, manufactured by Toyobo Co., Ltd.) and a general aluminum vapor-deposited polyester film 5 (VM-PET 1310, manufactured by Toray Film Processing Co., Ltd.) were prepared. The catalog values of the physical properties of films 4 and 5 are also shown 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 polyester films (PET films) manufactured from raw materials obtained from conventional fossil fuels. ) It can be seen that even if compared with 3-5, it has comparable physical properties.

Example 1
<Preparation 1 of laminated body>
One side of the biomass PET film 1 (thickness 12 μm) obtained as described above was subjected to corona treatment. And on the corona-treated surface of the biomass PET film 1, polylactic acid (derived from biomass, manufactured by Unitika: Terramac TP-4000) and low-density polyethylene (made by Ube Maruzen Polyethylene: Z568) via an anchor coating agent containing polyethyleneimine The blend film (blend ratio 6: 4, thickness 40 μm) was extruded at a resin temperature of 240 ° C. to obtain a laminated film. This laminated film had a layer structure as shown in FIG. Using this laminated film, a pillow bag having an outer dimension of 100 mm × 150 mm and a back seal width of 10 mm was prepared.

Example 2
<Preparation of laminate 2>
One side of the biomass PET film 1 (thickness 12 μm) obtained as described above was subjected to corona treatment, and aluminum was deposited on the corona treatment surface (deposition conditions: deposition source: aluminum, vacuum in the deposition chamber) Degree: 2 × 10 ⁻³ mbar, degree of vacuum in the winding chamber: 3 × 10 ⁻² mbar, film conveyance speed: 350 m / min, film thickness: 450 mm). In addition, a polylactic acid film (derived from biomass, manufactured by Mitsui Chemicals, Inc .: Pal Green, thickness 15 μm) was prepared, and one side was subjected to corona treatment to form a printing layer (pattern and white press) on the corona treatment surface. And the vapor deposition surface of the biomass PET film 1 and the printing surface of this polylactic acid film were bonded by dry lamination. Furthermore, the other surface of the biomass PET film 1 (surface opposite to the vapor deposition surface) and a general linear low-density polyethylene film (Mitsui Chemicals Tosero Co., Ltd .: TUX FC-D, thickness 80 μm) Were laminated by dry lamination to obtain a laminated film. The printing ink used was New LP Super manufactured by Toyo Ink.
A urethane-based adhesive (Mitsui Chemicals Co., Ltd .: Takerak A-515V / Takenate A-5) was used for bonding by dry lamination, and the coating amount during drying was adjusted to 3.5 g / m ² . After pasting, 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 having an outer dimension of 100 mm × 140 mm, a folding width of 30 mm, and an outer peripheral seal width of 5 mm was prepared.

Comparative Example 1
<Production 3 of Laminate>
One side of the general PET film 4 (thickness 12 μm) prepared above was subjected to corona treatment. And on the corona-treated surface of the PET film 4, polylactic acid (derived from biomass, manufactured by Unitika: Terramac TP-4000) and low-density polyethylene (made by Ube Maruzen Polyethylene: Z568) via an anchor coating agent containing polyethyleneimine. The blend film (blend ratio 6: 4, thickness 40 μm) was extruded at a resin temperature of 240 ° C. to obtain a laminated film.
This laminated film had a layer structure as shown in FIG. Using this laminated film, a pillow bag having an outer dimension of 100 mm × 150 mm and a back seal width of 10 mm was prepared.

Comparative Example 2
<Fabrication 4>
A polylactic acid film (derived from biomass, manufactured by Mitsui Chemicals, Inc .: Pal Green, thickness 15 μm) was prepared, and one side was subjected to corona treatment, and a printing layer (pattern and white press) was formed on the corona treatment surface. And the vapor deposition surface of the general aluminum vapor deposition PET film 5 (thickness 12 micrometers) prepared above and the printing surface of this polylactic acid film were bonded by dry lamination. Furthermore, the surface opposite to the vapor deposition surface of the aluminum vapor-deposited PET film 5 and a general linear low-density polyethylene film (Mitsui Chemicals Tosero Co., Ltd .: TUX FC-D, thickness 80 μm) are dry laminated. Bonding was performed to obtain a laminated film. The printing ink used was New LP Super manufactured by Toyo Ink. A urethane-based adhesive (Mitsui Chemicals Co., Ltd .: Takerak A-515V / Takenate A-5) was used for bonding by dry lamination, and the coating amount during drying was adjusted to 3.5 g / m ² . After pasting, 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 having an outer dimension of 100 mm × 140 mm, a folding width of 30 mm, and an outer peripheral seal width of 5 mm was prepared.

<Evaluation of laminate>
Each laminated film obtained in Example 1 and Comparative Example 1 was cut into a width of 15 mm and a length of 200 mm to obtain a test piece. The seal layer surfaces of the test pieces were bonded together by heat sealing. The peeled strength at the time of T was measured using a tensile tester (Tensilon RTC-125A, manufactured by Orientec Co., Ltd.). The sealing pressure in this measurement 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 measurement was performed according to JIS Z1707. The measurement results were as shown in Table 2 below.

  Each laminated film 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 polylactic acid film 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. Further, the PET film and the polyethylene film were peeled, and the peel strength at T was measured under the same conditions. Each measurement result was as shown in Table 3 below.

  The sealing strength of each laminated film obtained in Example 2 and Comparative Example 2 was measured under the same conditions as described above. The measurement results were as shown in Table 3 below.

Each standing pouch obtained in Example 2 and Comparative Example 2 was filled with 80 cc of water, and then the opening (upper edge) was sealed to prepare a standing pouch with water. The produced standing pouch with water was dropped upright from a height of 50 cm, and a drop impact test was performed. The measurement results were as shown in Table 3 below.

  As is clear from Tables 2 and 3, the laminate having a layer made of a polyethylene terephthalate film synthesized using biomass-derived ethylene glycol is compared with a laminate having a layer made of an existing polyester film. It can be seen that it has inferior physical properties.

DESCRIPTION OF SYMBOLS 10 Laminate 11 1st layer 12 2nd layer 20 Laminate 21 1st layer 22 2nd layer 23 3rd layer 24 Adhesive layer 25 Print layer 26 4th layer

Claims (18)

A laminate having at least a first layer and a second layer,
The first layer is composed of a resin composition comprising as a main component a polyester composed of a diol unit and a dicarboxylic acid unit, and the resin composition is ethylene glycol derived from biomass and having a dicarboxylic acid unit. Comprising polyester, a dicarboxylic acid derived from fossil fuel,
The second layer, polylactic acid, a polyethylene, a polypropylene, characterized by comprising a polytrimethylene terephthalate, and one or a resin material containing two or more of the biomass-derived feedstock is selected from the group consisting of polyethylene terephthalate, Laminated body.   The resin composition further comprises a polyester obtained by recycling a resin product comprising 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. The laminate according to claim 1, comprising:   The laminate according to claim 2, wherein the resin composition comprises 5 to 45 mass% of the polyester obtained by the recycling with respect to the entire resin composition.   The laminate according to any one of claims 1 to 3, wherein the dicarboxylic acid derived from the fossil fuel is terephthalic acid.   The laminate according to claim 1, wherein the resin composition further comprises an additive.   The laminate according to claim 5, wherein the resin composition comprises 5 to 50% by mass of the additive with respect to the entire resin composition.   The additives include plasticizers, UV stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, yarn friction reducing agents, mold release agents, antioxidants, and ion exchange. The laminate according to claim 5 or 6, which is one or more selected from the group consisting of an agent and a color pigment.   The laminate according to any one of Claims 1 to 7, wherein the content of carbon derived from biomass by radioactive carbon (C14) measurement is 10 to 19% with respect to the total carbon in the resin composition. .   The laminate according to any one of claims 1 to 8, wherein the first layer is a biaxially stretched resin film.   The laminate according to any one of claims 1 to 9, further comprising a third layer containing an inorganic substance.   The laminated body as described in any one of Claims 1-10 which further has a 4th layer containing resin obtained from the raw material derived from a fossil fuel.   The laminate according to any one of claims 1 to 11, further comprising a paper layer.   The laminate according to any one of claims 1 to 12, wherein the laminate has a printed layer on the surface of any one of the first to fourth layers or two or more layers.   The laminated film which consists of a laminated body as described in any one of Claims 1-13.   The packaging bag which consists of a laminated body as described in any one of Claims 1-13.   The label material which consists of a laminated body as described in any one of Claims 1-13.   The cover material which consists of a laminated body as described in any one of Claims 1-13.   The laminated tube which consists of a laminated body as described in any one of Claims 1-13.

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